 COMPOSITION, DETERGENT, CLEANING, DISINFECTANT OR BLASTING COMPOSITION, GRANULA, PROCESS FOR STAININ
专利摘要:
composition, detergent, cleaning composition, disinfectant or bleach, granule, process for bleaching stains or dirt in textile materials, and use of the compound of the present invention relates to specific acylidrazone compounds for use as oxidation catalysts and a process to remove stains and dirt on textiles and hard surfaces. The compounds are replaced by a specific cyclic ammonium group adjacent to the acyl group. Additional aspects of the invention are compositions or formulations comprising such compounds. 公开号:BR112013014591B1 申请号:R112013014591-9 申请日:2011-12-08 公开日:2019-04-16 发明作者:Hauke Rohwer；Barbara Wagner；Frédérique Wendeborn；Katharina Misteli 申请人:Basf Se； IPC主号:
专利说明:
“COMPOSITION, DETERGENT, CLEANING COMPOSITION, DISINFECTANT OR BLeach, GRANULE, PROCESS FOR THE STAINING OF STAINS OR DIRT IN TEXTILE MATERIALS, AND, USE OF COMPOUND” [001] The present invention concerns specific acylhydrazone compounds, their use as oxidation catalysts and a process to remove stains and dirt on textiles and hard surfaces. The compounds are replaced by a specific cyclic ammonium group adjacent to the acyl group. Additional aspects of the invention are compositions or formulations that comprise such compounds. [002] Metal complex catalysts with hydrazide ligands have generally been described as oxidation catalysts, for example, in DE 196 39 603. However, the disclosed compounds are not active enough. [003] In WO 2009/124855, metal complex compounds have hydrazide ligands, preferably with electron withdrawal groups adjacent to the acyl group are described. The respective acylhydrazone ligands and their use are also described. The present compounds differ from those described in WO 2009/124855 in being replaced by a specific cyclic ammonium group adjacent to the acyl group. This specific substitution pattern guarantees a substantially higher bleach activity compared to the prior art complexes or ligands. [004] The present compounds are used especially for intensifying the action of H2O2 or peroxides, for example, in the treatment of textile materials, without, at the same time, causing any estimated damage to fibers and dyes. There is also no estimated damage to fibers and dyes if these compounds are used in combination with an enzyme or a mixture of enzymes. Petition 870180071085, of 08/14/2018, p. 11/76 2/52 [005] The present compounds can also be used as the catalysts for oxidation using molecular oxygen and / or air, that is, without peroxide compounds and / or peroxide-forming substances. The bleaching of the tissue can happen during and / or after the treatment of the fiber with the formulation, which comprises the compounds. [006] The compounds do not cause any odor during use and are significantly more efficient as bleach catalysts compared to the corresponding open chain tertiary amines. [007] Metal ions, such as aluminum, zinc, manganese, titanium, iron, cobalt, nickel or copper, for example, Al (III), Zn (II), Mn (II) (III) - (IV) - (V), Cu (I) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I ) - (II) (III), Ti (II) - (III) - (IV) or, for example, Mn (II) - (III) - (IV) - (V), Cu (I) - (II ) - (III), Fe (I) - (II) - (III) - (IV) and Co (I) - (II) - (III) may be present during the textile material treatment process but are not required for the improved targeting effect. [008] Bleaching agents containing peroxide have been used in washing and cleaning processes. These have an excellent action at a liquid temperature of 90 ° C and above, but their performance decreases noticeably at lower temperatures. Various transition metal ions added in the form of suitable salts and coordination compounds containing such cations are known to activate H2O2. In that way, it is possible that the bleaching effect, which is unsatisfactory at lower temperatures, of H2O2 or precursors that release H2O2 and other peroxo compounds, is increased. [009] The purpose of the present invention is, therefore, to provide improved metal-free catalysts for oxidation processes that satisfy the above requirements and, especially, intensify the action of peroxide compounds in most varied fields of application without causing any estimated damage . Petition 870180071085, of 08/14/2018, p. 12/76 3/52 [0010] One aspect of the invention is a compound of the formula (1) R5 R i HO HO R 6 R R R (1) where R1, R2, R3, R4 independently of one another are hydrogen, unsubstituted or substituted C1-C28 alkyl, C1-C28 alkoxy, C1-C28 alkenyl, C2-C22 alkynyl, C3-C12 cycloalkyl, C3-C12 cycloalkenyl, C7 aralkyl -C9, C3-C20 heteroalkyl, C1-C12 cycloetheroalkyl, C5-C16 heteroalkyl, unsubstituted or substituted phenyl or naphthyl, where the substituents for the radicals are selected from the group consisting of C1-C4 alkyl; C1-C4 alkoxy; hydroxy; sulfo; sulfate; halogen; cyan; nitro; carboxy; amino; N-mono- or N, N-di-C1-C4 amino substituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino in which the amino groups can be quaternized; phenyl; phenoxy or naphthyloxy; or R1, R2, R3, R4 independently of each other are OR11, NR11R12, NO2 or halogen; or R1 and R2, R2 and R3 or R3 and R4 are joined together to form 1, 2 or 3 carbocyclic or heterocyclic rings, which can be unbroken or interrupted by one or more -O-, -S- or -NR13- and / or that can still be fused with other aromatic rings and / or that can be replaced by one or more C1-C6 alkyl groups. R5 indicates hydrogen, unsubstituted or substituted C1-C28 alkyl, C1-C28 alkenyl, C2-C22 alkynyl, C3-C12 cycloalkyl, C3-C12 cycloalkenyl, C7-C9 aralkyl, C3-C20 heteroalkyl, C1-C12 cycloalkylalkyl, heteroalkyl -C16, unsubstituted or substituted phenyl or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C1-C4 alkyl; C1 alkoxyPetition 870180071085, from 08/14/2018, p. 13/76 4/52 C4 hydroxy; sulfo; sulfate; halogen; cyan; nitro; carboxy; amino; N-mono N, N-di-C 1 -C 4 alkyl unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino in which the amino groups can be quaternized; phenyl; phenoxy or naphthyloxy; R6 indicates hydrogen, C1-C28 alkyl, C1-C28 alkenyl, C2-C22 alkynyl, C3-C12 cycloalkyl, C3-C12 cycloalkenyl, C7-C9 aralkyl, C3-C20 heteroalkyl, C1-C12 cycloethylalkyl, C5-C16 heteroalkyl, C5-C16 heteroalkyl unsubstituted or substituted or naphthyl or heteroaryl unsubstituted or substituted; wherein the substituents for the radicals are selected from the group consisting of C1-C4 alkyl; C1-C4 alkoxy; hydroxy; sulfo; sulfate; halogen; cyan; nitro; carboxy; amino; N-mono- or N, N-di-C1-C4 amino substituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino in which the amino groups can be quaternized; phenyl; phenoxy or naphthyloxy; R7 is a group rrrr R io R io R io R io - (CH 2 ) -NO - (CH 2 ) -NS - (CH 2 ) —NI - (CH 2 ) —NI kx 7 , k /, k - ° or kv ' s each group with an A anion - ; k is an integer from 1 to 4; A - is an anion of an organic or inorganic acid; R10 indicates hydrogen, C1-C28 alkyl, C1-C28 alkenyl, C2-C22 alkynyl, C3-C12 cycloalkyl, C3-C12 cycloalkenyl, C7-C9 aralkyl, C3-C20 heteroalkyl, C1-C12 cycloethylalkyl, C5-C16 heteroalkyl; R11, R12 are independently hydrogen, C1-C18 alkyl or phenyl; or R11 and R12 together with the nitrogen atom to which they are attached form a 5- or 6-membered ring that may still contain an N, O or S atom. R13 indicates hydrogen or C1-C18 alkyl. Petition 870180071085, of 08/14/2018, p. 14/76 5/52 [0011] When applicable, the acyl hydrazone derivatives can be in their E or Z configuration. [0012] When R 6 is hydrogen, the compound of formula (1) can be in one of its tautomeric forms or as a mixture of its different tautomeric forms. [0013] The compounds of formula (1) can also be ligands in metal complexes, such as Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III), Fe (I) (II) - (III) - (IV), Co (I) - (II) - (III). These complexes can also be used in cleaning and bleaching processes, in particular, in the context of washing processes. Similar complexes and their use have been described in WO 91/224855 and WO 2009/124855. [0014] The inorganic or organic anion A - can be an anion, such as RCOO - , ClO4 - , BF4 - , PF6 - , RSO3 - , RSO4 - , SO4 2- , H2PO4 - , HPO4 2- , OCN - , SCN - , NO3 - , F - , Cl - , Br - or HCO3 - , with R being hydrogen, optionally substituted C1-C24 alkyl or optionally substituted aryl. Examples are lactic acid, citric acid, tartaric acid, succinic acid. [0015] For anions with a charge greater than -1, the charge balance is established by additional cations, such as H + , Na + , K + , NH4 + . [0016] For example, A - is RCOO - , ClO4 - , BF4 - , PF6 - , RSO3 - , RSO 4 - , SO4 2- , NO3 - , F - , Cl - , Br - and I - where R is linear or branched C1-C18 alkyl or phenyl. [0017] In general, unsubstituted alkyl, heteroalkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, phenyl, naphthyl, aralkyl, heteroaralkyl and cycloheteroalkyl are preferred. [0018] Cyclic substituents are preferably 5, 6 or membered rings, 6-membered rings are preferred. [0019] Arila is phenyl or naphthyl in all cases when applicable. [0020] The mentioned C1-C18 alkyl radicals for the compounds of the formula (1) are, for example, straight or branched alkyl radicals, such as Petition 870180071085, of 08/14/2018, p. 15/76 6/52 such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or pentyl, straight or branched, hexyl, heptyl or octyl. Preference is given to C 1 -C 12 alkyl radicals, especially C 1 -C 8 alkyl radicals and preferably C 1 -C 4 alkyl radicals. The alkyl radicals mentioned can be unsubstituted or substituted, for example, by hydroxy, C 1 -C 4 alkoxy, sulfo or sulfate, especially by hydroxy. Corresponding unsubstituted alkyl radicals are preferred. Very special preference is given to methyl and ethyl, especially methyl. [0021] In the compounds of the formulas (1) halogen is preferably chlorine, bromine or fluorine, with special preference being given to chlorine. [0022] Examples of aryl radicals that come into consideration for the compounds of formula (1) are phenyl or naphthyl each unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, cyano, nitro, , carboxy, sulfo, hydroxy, amino, N-mono- or N, N-dialkyl C 1 -C 4 amino unsubstituted or substituted by hydroxy in the alkyl, N-phenylamino, Nnaftilamino portion, where amino groups can be quaternized, phenyl, phenoxy or naphthyloxy. Preferred substituents are C1-C4 alkyl, C1-C4 alkoxy, phenyl and hydroxy. [0023] Special preference is given to the corresponding phenyl radicals. [0024] C 3 -C 12 cycloalkyl refers to saturated cyclic hydrocarbons. C3-C12 cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, mentila, thujila, bornila, 1adamantila or 2-adamantila. [0025] C2-C18 alkenyl is, for example, vinyl, allila, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten 3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4 pentadien-3-yl or means isomers other than hexenyl, octenyl, nonenyl, decenyl or dodecenyl. Petition 870180071085, of 08/14/2018, p. 16/76 7/52 [0026] C3-Ci 2 cycloalkenyl refers to unsaturated hydrocarbon residues containing one or multiple double bonds, such as, 2cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl , 3-cyclohexen-1-yl, 2,4-cycloexadien-1-yl, 1 - ^ - menten-8-yl, 4 (10) -thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl or 7,7-dimethyl-2,4-norcaradien-3-yl. [0027] C7-C9 aralkyl is, for example, benzyl, β-phenyl-ethyl, α, αdimethylbenzyl. [0028] C 5 -C 16 heteroalkyl means, for example, a C 1 -C 8 alkyl moiety which is replaced by a C 4 -C 8 heteroaryl group, preferably with a C5-C6 heteroraryl group. [0029] C5-C6 heteroaryl is, for example, pyridine or pyrimidine. [0030] In a specific embodiment, the compound is of the formula (1) R R (1) where R1, R2, R3, R4 independently of one another are hydrogen, C1-C8 alkyl, C1-C8 alkoxy, halogen, OR11 or NR11R12; R5 indicates hydrogen or C1-C18 alkyl; R6 indicates hydrogen or C1-C18 alkyl; R7 is a group - (CH 2 ) -N o R 10 t - (CH 2 ) -N + S k - / R 10 - (CH 2 ) —N R 10 - (CH 2 ) —N or each group with an A anion - ; k is an integer from 1 to 4; A - is Cl - , Br - , ClO 4 - , NO3 - , HSO4-, BF4 - or PF6 - ; R 10 indicates hydrogen or C 1 -C 18 alkyl; R 11 , R 12 are independently hydrogen, C 1 -C 18 alkyl or Petition 870180071085, of 08/14/2018, p. 17/76 8/52 phenyl; R13 indicates hydrogen or C1-C4 alkyl. For example, in the compounds of formula (1) R1, R2, R3, R4 independently of one another are hydrogen, OH, methoxy, halogen or methyl; R5 indicates hydrogen or methyl; R6 indicates hydrogen or methyl; R7 is a group - (CH 2 ) -N ok - / R i0 t - (CH 2 ) -N + S k - / R 10 - (CH 2 ) —N R 10 - (CH 2 ) —N or each group with an A anion - ; k is an integer from 1 to 2; A - is Cl - , Br - , ClO4 - , NO3 - , HSO4-, BF4 - or PF6 - ; R10 indicates hydrogen or C1-C4 alkyl. For example, in the compounds of formula (1) R1, R2, R3, R4 independently of one another are hydrogen, OH, or methyl; R5 indicates hydrogen; R6 indicates hydrogen; R7 is a group R 10 t - (CH 2 ) —N + O k ' R 10 - (CH 2 ) —N or each group with an A anion - ; k is 1; A - is Cl - , Br - , ClO4 - , NO3 - , HSO4-, BF4 - or PF6 - ; R10 indicates methyl. A compound of formula (1) in which R1, R2, R3, R4 are hydrogen is preferred; R5 indicates hydrogen; R6 indicates hydrogen; Petition 870180071085, of 08/14/2018, p. 18/76 9/52 R.7 is a group R <„ - (CH „) - N + X ok v_ ' R 10 - (CH 2 ) —N or each group with an A anion - ; k is 1; A - is Cl - or Br - , R10 indicates methyl. [0031] The compounds can be prepared according to standard procedures by reaction with a carbonyl compound, such as an aldehyde with a primary amine to form the corresponding Schiff's base, in particular, with a hydrazide and with a carbonyl compound in which substituents are as defined above. The compounds can, for example, be prepared in analogy to those described in WO 2009/124855. [0032] The compounds of formula (1) including the preferences described above are new compounds with the exception of (N - [(2hydroxyphenyl) methyleneamino] -2- (4-methylmorpholin-4-io-4-yl) acetamide chloride , which is excluded from the scope of the compounds according to formula (1) .The use of this specific compound, however, is also new. [0033] The compounds of formula (1) are useful as catalysts for oxidation reactions, for bleaching stains and dirt on textiles or for cleaning hard surfaces. [0034] Therefore, another aspect of the invention is a composition that comprises a) H2O2 or a precursor to H2O2 and b) a compound of formula (1) as described above. [0035] The amount of component b), composed of formula (1), in the composition can vary from 0.00001% by weight to 1% by weight, preferably from 0.0001% by weight to 0.1% by weight, based on weight of the total composition. Petition 870180071085, of 08/14/2018, p. 19/76 10/52 [0036] In many cases in the composition as described above, additional bleach activators are present. Suitable bleach activators are summarized below. [0037] The amount of bleach activator in the composition can vary from 0.1% by weight to 12% by weight, preferably from 0.5% by weight to 10% by weight, based on the weight of the total composition. This can be of advantage when the composition as described above optionally contains one or more metal chelating agents (scavengers), such as hydroxyethyldiphosphonate (HEDP). More generally, chelating agents suitable for use herein can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctional substituted aromatic chelating agents and mixtures thereof. Other chelating agents suitable for use in this are the commercial DEQUEST series and chelators from Nalco, Inc. [0039] Aminocarboxylates useful as optional chelating agents include ethylene diaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminoexacetates, diethylenetriamine-penta-acetates and these ethanalyglycosides and ethanololdines. [0040] Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions and include ethylene diaminetetraquis (methylene phosphonates). [0041] Additional biodegradable scavengers are, for example, amino acid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Baypure CX. [0042] Preferably, the aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Petition 870180071085, of 08/14/2018, p. 20/76 11/52 [0043] A highly preferable biodegradable chelator for use here is ethylenediamine disuccinate (“EDDS”). [0044] The following chelating agents (scavengers) are preferred: citric acid, oxalic acid, methyl-glycine-diacetic acid (MGDA), ethylenediamine-N, N'-disuccinic acid (EDDS), 1-hydroxy ethylidene-1,1diphosphonic acid (HEDP). [0045] If used, these selective transition metal chelating or sequestering agents, in general, will be present from about 0.001% by weight to about 10% by weight, more preferably from about 0.05% by weight to about 1% by weight, based on the weight of the total composition. [0046] Component a) of the composition can be H 2 O 2 , a precursor of H 2 O 2 or a peroxide-forming substance. H2O2 precursors are preferred, such as peroxides or peracids summarized below. [0047] As precursors of H 2 O 2 peroxides come into consideration. That is, each compound that is capable of producing hydrogen peroxide that is capable of producing hydrogen peroxide in aqueous solutions, for example, the organic and inorganic peroxides known in the literature and commercially available that targets textile materials at conventional washing temperatures, for example example, 10 to 95 ° C. [0048] Preferably, however, organic peroxides are used, for example, persulfates, perborates, percarbonates and / or persilicates. These are typically used in an amount of 2 to 80% by weight, preferably 4 to 30% by weight, based on the weight of the composition. [0049] Typically, the compound of formula (1) is present in the composition in an amount of 0.05 to 15% by weight, preferably 0.1 to 10% by weight, based on the weight of the total composition. [0050] Examples of suitable inorganic peroxides are sodium perborate tetrahydrate or sodium perborate monohydrate, sodium percarbonate, inorganic peroxyacid compounds, such as, for example, Petition 870180071085, of 08/14/2018, p. 21/76 12/52 example, potassium monopersulfate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, their amount will normally be in the range of about 2 to 80% by weight, preferably 4 to 30% by weight, based on the weight of the composition. [0051] Organic peroxides are, for example, mono- or polyperoxides, urea peroxides, a combination of a C1-C4 alkanol oxidase and C1-C4 alkanol (such as methanol oxidase and ethanol as described in WO95 / 07972), alkyl hydroxy peroxides, such as cumene hydroperoxide and t-butyl hydroperoxide. [0052] Peroxides can be a variety of crystalline forms and have different water contents and these can also be used together with other inorganic or organic compounds in order to improve their storage stability. [0053] As oxidants, peroxy acids can also be used. An example are organic mono peracids of the formula or iT co-om in which M means a hydrogen or a cation, R 19 means unsubstituted C 1 -C 18 alkyl; substituted C 1 -C 18 alkyl; unsubstituted aryl, substituted aryl; - (C 1 -C 6 alkylene) -aryl, where the alkylene and / or the alkyl group can be substituted and phthalimidoalkylene C 1 -C 8 , in which the phthalimido group and / or the alkylene group can be substituted. [0054] The preferred mono organic peroxy acids and their salts are those of the formula o r ^ c-o-om where M stands for hydrogen or an alkali metal and Petition 870180071085, of 08/14/2018, p. 22/76 13/52 R'i9 means C1-C4 alkyl; phenyl; C1-C2 alkylene-phenyl or C1-C8 phthalimidoalkylene. [0055] CH 3 COOOH and its alkaline salts are especially preferred. [0056] Also especially preferred is peroxy hexanoic ε-phthalimido acid and its alkaline sausages and its alkaline salts. [0057] Diperoxy acids, for example, acid, are also suitable 1,12-diperoxidodecanedioic acid (DPDA), 1,9-diperoxiazelaic acid, diperoxybasilic acid, diperoxysebasic acid, diperoxyisophthalic acid, 2decildiperoxybutane-1,4-diotic acid and 4,4'-sulfonylbisperoxybenzoic acid. [0058] In some cases, the use of an additional bleach activator may be advantageous. [0059] The term bleach activator is often used as a synonym for peroxyacid bleach precursor. All of the peroxy compounds mentioned above can be used alone or in conjunction with a peroxyacid bleach precursor. [0060] Such precursors are the corresponding carboxyacids or the corresponding carboxyanhydride or the corresponding carbonyl chloride or amides or esters, which can form the peroxyacids in perhydrolysis. Such reactions are commonly known. [0061] Peroxyacid bleach precursors are known and widely described in the literature, such as in British Patents 836988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A0185522; EP-A-0174132; EP-A-0120591 and U. S. Patents No. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393. [0062] Suitable bleach activators include bleach activators, which carry unsubstituted or substituted O- and / or N-acyl groups and / or benzoyl groups. Preference is given to polyacetylated alkylenediamines, especially tetraacetylethylenediamine (TAED); acetylated glycolurils, especially tetraacetyl glycol urea (TAGU), N, N-diacetyl-N, N Petition 870180071085, from 08/14/2018, p. 23/76 14/52 dimethylurea (DDU); sodium-4-benzoyloxy benzene sulfonate (SBOBS); sodium1-methyl-2-benzoyloxy benzene-4-sulfonate; sodium-4-methyl-3-benzoloxy benzoate; trimethyl ammonium toluyloxy-benzene sulfonate; acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexyl-1,3,5-triazine (DADHT); compounds of the formula (6): R 21 O (10) where R22 is a sulfonate group, a carboxylic acid group or a carboxylate group and where R 21 is straight or branched (C 7 -C 15 ) alkyl, especially activators known under the names SNOBS, SLOBS and DOBA; acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-di-idrofuran and also acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), penta -acetylfructose, tetraacetylxylose and octaacetillactose as well as optionally glucamine Nakylated acetylated and gluconolactone. It is also possible to use the combinations of conventional bleach activators known from German Patent Application DE-A-44 43 177. Nitrile compounds that form acids with peroxides are also considered as bleach activators. [0063] Another useful class of peroxyacid bleaching precursors is that of cationic precursors, i.e. peroxyacid substituted by quaternary ammonium as disclosed in US Patent No. 4,751,015 and 4,397,757, in EP-A0284292 and EP-A-331,229. Examples of peroxyacid bleach precursors of this class are: 2- (N, N, N-trimethyl ammonium) ethyl sodium 4-sulfonphenyl carbonate - (SPCC), N-octyl chloride, N, N-dimethyl-N10 carbophenoxy decyl ammonium - (ODC), 3- (N, N, N-trimethyl ammonium carboxylate) Petition 870180071085, of 08/14/2018, p. 24/76 15/52 propyl sodium-4-sulfophenyl carboxylate and N, N, N-trimethyl ammonium toluyloxy benzene sulfonate. [0064] Another special class of bleach precursors is formed by cationic nitriles as disclosed in EP-A-303,520, WO 96/40661 and in European patent specification No. 458,396, 790244 and 464,880. These cationic nitriles also known as nitrile quats have the formula x - O II “C = N (α) R 33 ^^ ( CH 2) n - ^^ N R R X - ( γ) -N- (CH2) n'-N 2X - C ^ N (δ) where R30 is C1-C24 alkyl; a C1-C24 alkenyl; an aralkyl having a C1-C24 alkyl; a substituted C1-C24 alkyl; a substituted C1-C24 alkenyl; a substituted arila, R31 and R32 are each, independently a C1-C3 alkyl; hydroxyalkyl having 1 to 3 carbon atoms, - (C2H4O) nH, n being 1 to 6; CH2-CN R33 is C1-C20 alkyl; a C1-C20 alkenyl; a substituted C1C20 alkyl; a substituted C1-C20 alkenyl; an aralkyl having a C1-C24 alkyl and at least one other substituent, R34, R35, R36, R37 and R38 are each independently hydrogen, a C1-C10 alkyl, a C1-C10 alkenyl, a substituted C1-C10 alkyl, a substituted C1-C10 alkenyl, carboxyl, sulfonyl or cyano R38, R39, R40 and R41 are each, independently an alkyl C1-C6, n 'is an integer from 1 to 3, n' 'is an integer from 1 to 16 and Petition 870180071085, of 08/14/2018, p. 25/76 16/52 X is an anion. Other nitrile quats have the following formula xi 45 Rj ^ —f-CEN R 44 R 46 (ε) where R42 and R43 form, together with the nitrogen atom to which they are attached, a ring comprising 4 to 6 carbon atoms, this ring can also be replaced by C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkanoyl, phenyl, amino, ammonium, cyano, cyanamino or chlorine and 1 or 2 carbon atoms in this ring can also be replaced by an oxygen atom, an N-R47 group and / or an R44-N-R47 group, where R47 is hydrogen, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, phenyl, C7-C9 aralkyl, C5-C7 cycloalkyl, C1-C5 alkanoyl, cyanomethyl or cyan, R44 is C1-C24 alkyl, preferably C1-C4 alkyl; C2-C24 alkenyl, preferably C2-C4 alkenyl, cyanomethyl or C1-C4 alkoxy C1-C4 alkyl, R45 and R46 are, independently of each other hydrogen; C1-C4 alkyl; C1-C4 alkenyl; C1-C4 alkoxy C1-C4 alkyl; phenyl or C1-C3 alkylphenyl, preferably hydrogen, methyl or phenyl, so preferably, the R45 portion means hydrogen, if R46 is not hydrogen and X - is an anion. [0065] Suitable examples of nitrile quats of formula (□) are / - ^ C ^ NO + N X ch 3 Petition 870180071085, of 08/14/2018, p. 26/76 17/52 -ΟΞΝ CH. O II HO-S II O O II HO-S II O O II HO-S II O // ch 3 CH, CH other nitrile qats have the formula R48 X- NC _ C = N '49 R. ( η) R 47 RX | R 48 X N 1 + C ^ N A 1 I R 49 (Φ) R '„ N — C — C = N R ' X - where A is a saturated ring formed by a plurality of atoms in addition to the atom of N1, the saturated ring atoms include at least one carbon atom and at least one heteroatom in addition to the atom of N1, said a hetero atom of the group consisting of atoms of O, S and N, the R47 substituent attached to the N1 atom of the structure of Formula (φ) is (a) a C1-C8 alkyl or alkoxylated alkyl where the alkoxy is C2-4, (b) a C4-C24 cycloalkyl , (c) a C7-C24 alkaryl, (d) a repeat or non-repeat alkoxy or alkoxylated alcohol, where the alkoxy unit is C2-4 or (e) -CRs0R51-C = N where R50 and R51 are each an H, a C1-C24 alkyl, cycloalkyl or alkaryl or a repeat or non-repeat alkoxyl or alkoxylated alcohol where the alkoxy moiety is C2C 4 , in Formula (□) at least one of the R 48 and R 49 substituents is H and the another of R 48 and R 49 is H, a C 1 -C 24 alkyl, cycloalkyl or alkaryl or an alkoxy Petition 870180071085, of 08/14/2018, p. 27/76 18/52 repetition or non-repetition or alkoxylated alcohol where the alkoxy unit is C2-4 and Y is at least one counter ion. [0066] In a preferred embodiment of the invention the compounds of formula (1) are used together with a peroxide or peroxide precursor and a bleach activator that is selected from the group consisting of tetraacetylethylenediamine, pentaacetylglucose, octaneyloxybenzenesulfonate , sodium nonanoyloxybenzenesulphonate, sodium decanoyloxybenzenesulphonate, undecanoiloxibenzenossulfonato sodium, sodium dodecanoiloxibenzenossulfonato, octanoiloxibenzoico acid nonanoiloxibenzoico pacido, decanoiloxibenzoico acid undecanoiloxibenzoico acid dodecanoiloxibenzoico acid octanoiloxibenzeno, nonanoyloxybenzene, decanoiloxibenzeno, and undecanoiloxibenzeno dodecanoiloxibenzeno. [0067] Activators can be used in an amount of up to 12% by weight, preferably from 0.5 to 10% by weight based on the total weight of the composition. [0068] Since the compounds of the invention are used for bleaching stains or dirt on textile materials or dishes in the context of a washing process or by the direct application of a stain remover, an additional aspect of the invention is a detergent composition , cleaning or bleach that comprises I) 0 to 50% by weight, based on the total weight of the composition, A) at least one anionic surfactant and / or B) one anionic surfactant, II) from 0 to 70% by weight, based on the total weight of the composition, C) at least one forming substance, III) from 1 to 99% by weight, based on the total weight of the composition, D) at least one peroxide and / or a peroxide activator, O2 and / or air, IV) E) at least one compound of the formula (1) according to Petition 870180071085, of 08/14/2018, p. 28/76 19/52 claims 1 to 5 in an amount that, in the liquid, gives a concentration of 0.5 to 100 mg / liter of liquid, when from 0.5 to 50 g / liter of the detergent, cleaning agent, disinfectant or bleach are added to the liquid, V) from 0 to 20% by weight, based on the total weight of the composition, of at least one additional additive and VI) water ad 100% by weight, based on the total weight of the composition. [0069] The composition may also contain water or a filling material, such as Na 2 SO 4 . The sum of components I) to IV) and optionally the additional components increases to 100%. [0070] Every weight% is based on the total weight of the detergent, cleaning or bleaching composition. [0071] The detergent, cleaning or bleaching compositions can be of any type of industrial or household cleaning or bleaching formulation. [0072] Detergents can be in solid, liquid, gel-like or paste-like form. Detergents can also be in the form of powders or (super-) powders or granules, in the form of single or multiple layer tablets (tabs), in the form of washing agent bars, washing agent blocks, agent sheets washing agents, washing agent pastes or in the form of powders, pastes, gels or liquids used in capsules or bags (sachets). [0073] When the composition is used in a washing process, the concentration of H2O2 or its precursor, such as perborate or percarbonate can vary in the range of 0.01 g / L to 15 g / L, preferably 0.03 g / L L to 8 g / L and more preferably 0.05 g / L to 2.5 g / L. if an additional activator is used, the activator, such as tetraacetylethylenediamine can range from 0.01 g / L to 5 g / L, preferably from 0.015 g / L to 3 g / L, more preferably from 0.015 g / L to 1 g / L. The compound of formula (1) can vary from 1 qmol / L to Petition 870180071085, of 08/14/2018, p. 29/76 20/52 mmol / L, preferably from 3 pmol / L to 0.5 mmol / L, more preferably from 5 pmol / L to 0.3 mmol / L. [0074] It is also possible to use additional bleach catalysts, which are commonly known, for example, transition metal complexes as disclosed in EP 1194514, EP 1383857 or WO04 / 007657. [0075] When the detergent compositions according to the invention comprise a component A) and / or B), the amount of these is preferably from 0.5 to 50% by weight, especially from 0.5 to 30% by weight. [0076] When the detergent compositions according to the invention comprise a component C), the amount of these is preferably from 1 to 70% by weight, especially from 1 to 50% by weight. Special preference is given to an amount of 5 to 50% by weight and especially an amount of 10 to 50% by weight. [0077] The detergent composition according to the invention can be, for example, a heavy detergent containing peroxide or a separate bleach additive or a stain remover that must be applied directly. A bleach additive is used to remove colored stains on textiles in a separate liquid before being washed with a detergent. A bleach additive can also be used in a liquid along with a detergent. [0078] Stain removers can be applied directly to the textile in question and are used especially for pre-treatment in the event of heavy local dirt. [0079] The stain remover can be applied in liquid form, by a spray method or in the form of a solid substance, such as a powder, especially as a granule. [0080] Anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof. Preference is given to alkylbenzenesulfonates, alkyl sulfates, alkyl ether Petition 870180071085, of 08/14/2018, p. 30/76 21/52 sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or an α-sulfonic fatty acid salt or an ester thereof. Preferred sulfonates are, for example, alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having 8 to 18 carbon atoms in the alkyl radical, alkyl ether sulfates having 8 to 18 carbon atoms in alkyl radical and fatty acid salts derived from palm oil or tallow and having 8 to 18 carbon atoms in the alkyl portion. The average molar number of ethylene oxide units added to the alkyl ether sulfates is 1 to 20, preferably 1 to 10. The cation in anionic surfactants is preferably an alkali metal cation, especially sodium or potassium, more especially sodium. Preferred carboxylates are alkali metal sarcosinates of the formula R 19 -CON (R 20 ) CH 2 COOM 1 where R 19 is C 9 C 17 alkyl or C 9 -C 17 alkenyl, R 2 o is C 1 -C 4 alkyl and M 1 is an alkali metal, especially sodium. [0082] The nonionic surfactant B) can be, for example, a primary or secondary alcohol ethoxylate, especially an ethoxylated C8-C20 aliphatic alcohol with an average of 1 to 20 mol of ethylene oxide per group of alcohol. Preference is given to primary or secondary C 10 -C 1 5 aliphatic alcohols with an average of 1 to 10 mol of ethylene oxide per alcohol group. Non-ethoxylated nonionic surfactants, for example, alkyl polyglycosides, glycerol monoethers and polyhydroxyamides (glucamide), can also be used. [0083] The total amount of anionic or non-ionic surfactants is 3 to 50% by weight, especially from 5 to 40% by weight and more especially from 5 to 30% by weight. The lower limit of those surfactants to which even greater preference is given is 5% by weight. [0084] When forming substance C) takes into account, for example, alkali metal phosphates, especially tripolyphosphates, carbonates Petition 870180071085, of 08/14/2018, p. 31/76 22/52 and hydrogen carbonates, especially their sodium salts, silicates, aluminum silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylene polyols (alkylen phosphonates) and mixtures of such compounds. [0085] Silicates that are especially suitable are sodium salts of silicate in crystalline layers of the formula NaHSi t O 2t + 1 .pH 2 O or Na 2 Si t O 2t + 1 .pH 2 O where t is a number of 1.9 to 4 and p is a number from 0 to 20. [0086] Among aluminum silicates, preference is given to those commercially available under the names zeolite A, B, X and HS and also to mixtures comprising two or more of such components. Special preference is given to zeolite A. [0087] Among polycarboxylates, preference is given to polyhydroxycarboxylates, especially citrates and acrylates and also to copolymers of these with maleic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediamine-tetraacetic acid and ethylenediamine disuccinate in racemic or enantiomerically pure (S, S) form. [0088] Biodegradable options are, for example, amino acid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Baypure CX (Lanxess). [0089] Phosphonates or aminoalkylenepoly (alkylenephosphonates) that are especially suitable are alkali metal salts of 1hydroxyethane-1,1-diphosphonic acid, nitrilotris (methylenephosphonic acid), ethylenediaminetetramethylenophosphonic acid and also their diethylenetriamine and phenylsetamine and phenylenetamethoxyamide. Also, preferred polyphosphonates have the following formula R 18 Ri8-N- (CH 2 CH 2 N) d -R 18 I R 18 Petition 870180071085, of 08/14/2018, p. 32/76 23/52 where Ris is CH2PO3H2 or a water-soluble salt thereof and d is an integer of the value 0, 1, 2 or 3. [0090] Polyphosphonates are especially preferred where d is an integer of the value of 1. [0091] The compositions may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example, from the classes of bis-triazinylamino-stilbenedisulfonic acid, bistriazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis- benzofuranylbiphenyl, derived from α bis-benzoxalyl, derived from bis-benzimidazolyl or derived from coumarin or a derivative of pyrazoline. [0092] The compositions can still comprise one or more additional additives. Such additives are, for example, for example, dirt suspending agents, for example, sodium carboxymethylcellulose; pH regulators, for example, alkali metal or alkaline earth metal silicates; foam regulators, for example, soap; salts for adjusting spray drying and granulation properties, for example, sodium sulfate; perfumes and also, if appropriate, anti-static and softening agents such as, for example, smectite; bleaching agents; pigments and / or toning agents. These constituents must be especially stable to any usable targeting agent. [0093] If the detergent composition is used in an automatic rat washer it is also common to use silver corrosion inhibitors. [0094] Such auxiliaries are added in a total amount of 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, especially from 0.5 to 5% by weight, based on the total weight of the formulation of detergent. [0095] In addition, the detergent can also optionally comprise enzymes. Enzymes can be added for the purpose of stain removal. Enzymes usually improve the action on spots Petition 870180071085, of 08/14/2018, p. 33/76 24/52 caused by protein or starch, such as, for example, blood, milk, grass or pilfer juices. Preferred enzymes are cellulases and proteases, especially proteases. Cellulases are enzymes that react with cellulose and its derivatives and hydrolyze them to form glucose, cellobiose and celleloigosaccharides. Cellulases remove dirt and, in addition, have the effect of intensifying the soft handling of the fabric. [0096] Examples of custom enzymes include, but are not limited to, the following: proteases as described in US-B-6 242 405, column 14, lines at 32; lipases as described in US-B-6 242 405, column 14, lines at 46; amylases as described in US-B-6 242 405, column 14, lines at 56 and cellulases as described in US-B-6 242 405, column 14, lines at 64. [0097] Commercially available detergent proteases, such as Alcalase ® , Esperase ® , Everlase ® , Savinase ® , Kannase ® and Durazym ® , are sold, for example, by NOVOZYMES A / S. [0098] Commercially available detergent amylases, such as Termamyl®, Duramyl®, Stainzyme®, Natalase®, Ban® and Fungamyl®, are sold, for example, by NOVOZYMES A / S. [0099] Commercially available detergent cellulases, such as Celluzyme ® , Carezyme ® and Endolase ® , are sold, for example, by NOVOZYMES A / S. [00100] Commercially available detergent lipases, such as Lipolase ® , Lipolase Ultra ® and Lipoprime ® , are sold, for example, by NOVOZYMES A / S. Petition 870180071085, of 08/14/2018, p. 34/76 25/52 [00101] Suitable mannanases, such as Mannanaway®, are sold by NOVOZYMES A / S. [00102] In addition to laundry care products, in a dish washing detergent, especially in a composition used in automatic dishwashers, the following enzymes are also commonly used: proteases, amylases, pullulanases, cutinases and lipases, for example, proteases, such as BLAP ® , Optimase ® , Opticlean ® , Maxacal ® , Maxapem ® , Esperase ® and / or Savinase ® , amylases such as Termamyl ® , Amylase-LT ® , Maxamyl ® and / or Duramyl ® , lipases such as Lipolase ® , Lipomax ® , Lumafast ® and / or Lipozym ® . Enzymes that can be used can, as described, for example in International Patent Applications WO 92/11347 and WO 94/23005, be absorbed into carriers and / or included in encapsulating substances in order to protect them from premature inactivation. These are present and cleaning formulations according to the invention preferably in amounts that do not exceed 5% by weight, especially in amounts from 0.1% by weight to 1.2% by weight. [00103] Amylases: The present invention preferably makes use of amylases having improved detergent stability, especially improved oxidative stability. Such amylases are not limited by the following: (a) An amylase according to WO 94/02597, Novo Nordisk A / S, published on February 3, 1994, as further illustrated by a mutant in which the substitution is made, using alanine or threonine (preferably threonine), from the methionine residue located at position 197 of B. licheniformis alpha-amylase, known as TERMAMYL ® or the variation of the homologous position of a similar precursor amylase, such as B. amyloliquefaciens, B .subtilis or B.stearothermophilus; (b) stability-enhanced amylases as described by Genencor International in a document entitled “Oxidatively Resistant alpha-Amylases” present at the 207th American Chemical Society National Meeting, March 13-17, Petition 870180071085, of 08/14/2018, p. 35/76 26/52 1994, by C. Mitchinson. It was observed that bleaches in dishwashing detergents inactivate alpha-amylases but that they improve amylases of oxidative stability were made by Genencor from B. licheniformis NCIB8061. Any other amylase enhanced by oxidative stability can be used. [00104] Proteases: protease enzymes are usually present in preferred embodiments of the invention at levels between 0.001% by weight and 5% by weight. The proteolytic enzyme can be of animal, vegetable or microorganism origin (preferred). Serine proteolytic enzyme of bacterial origin is most preferred. Purified or unpurified forms of enzyme can be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, when they are close to structural enzyme variants. Suitable proteolytic enzymes include Alcalase ® commercially, Esperase, Durazyme®, Savinase®, MAXATASE®, MAXACAL® and MAXAPEM® 15 (protein engineered Maxacal). Purafect® and subtilisin BPN and BPN 'are also commercially available. [00105] When present, lipases comprise from about 0.001% by weight to about 0.01% by weight of the present compositions and are optionally combined with about 1% by weight to about 5% by weight of a surfactant having dispersing properties of limestone soap, such as an alkyldimethylamine N-oxide or a sulfobetaine. The lipases suitable for use here include those of bacterial, animal and fungal origin, including those of chemically or genetically modified mutants. [00106] When lipases are incorporated in the present compositions, their stability and effectiveness may, in certain examples, be enhanced by combining small amounts (for example, less than 0.5% by weight of the composition) of oily material but not hydrolyzer. Petition 870180071085, of 08/14/2018, p. 36/76 27/52 [00107] Enzymes, when used, can be present in a total amount of 0.01 to 5% by weight, especially from 0.05 to 5% by weight and more especially from 0.1 to 4% in weight based on the total weight of the detergent formulation. [00108] If the detergent formulation is a dishwashing and dish detergent formulation, more preferably an automatic dishwashing detergent formulation, optionally these can also comprise from about 0.001% by weight to about 10% by weight, preferably from about 0.005% by weight to about 8% by weight, more preferably from about 0.01% by weight to about 6% by weight of an enzyme stabilizing system. The enzyme stabilizing system that is compatible with the enzyme detersive. Such a system can be inherently supplied by other formulation assets or added separately, for example by the formulator or a detergent-ready enzyme manufacturer. Such stabilizing systems may, for example, comprise calcium ion, boric acid, propylene glycol, short-chain carboxylic acids, boronic acids, and mixtures thereof and are designed to address different stabilization problems depending on the type and physical form of the detergent composition . [00109] In order to intensify the bleaching action, the compositions, in addition to understanding the catalysts described here, also comprise photocatalysts of the action that is based on the generation of simple oxygen. [00110] Other preferred additives for the compositions according to the invention are pigment fixing agents and / or polymers, during the washing of textiles, avoid the dyeing caused by the pigments in the washing liquid that was released from the textiles during the washing conditions . Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine-N-oxides, which can be modified by the incorporation of Petition 870180071085, of 08/14/2018, p. 37/76 28/52 anionic or cationic substituents, especially those having a molecular weight in the range of 5000 to 60,000, more especially 10,000 to 50,000. Such polymers are usually used in a total amount of 0.01 to 5% by weight, especially 0.05 to 5% by weight, more especially 0.1 to 2% by weight, based on the total weight of the formulation of detergent. Preferred polymers are those mentioned in WO-A-02/02865 (see especially page 1, last paragraph and page 2, first paragraph) and those in WO-A-04/05688. [00111] When the inventive detergent composition is used as a hard surface cleaner, especially when the composition is used in automatic dishwashing formulations then it has been observed that it is preferable to avoid using calcium precipitation soaps as defoamers in present composition when they tend to deposit on the dishes. In fact, phosphate esters are not entirely free from such problems and the formulator in general will choose to minimize the amount of antifoams that are potentially deposited in the present compositions. [00112] Other examples of foam suppressants are paraffin, paraffin / alcohol combinations, or bisgraphic acid amides. [00113] Dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations here may optionally also contain one or more heavy metal chelating agents, such as hydroxyethyldiphosphonate (HEDP). More generally, chelating agents suitable for use here can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctional substituted aromatic chelating agents and mixtures thereof. Other chelating agents suitable for use in this are the serious commercial DEQUEST and chelators from Nalco, Inc. [00114] Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminatriacetates, Petition 870180071085, of 08/14/2018, p. 38/76 29/52 nitrilotriacetates, ethylenediamine tetraproprionates, triethylene tetraaminehexacetates, diethylene triamine-pentaacetates and ethanoldiglycines, alkali metal, ammonium and ammonium salts substituted thereof and mixtures thereof. [00115] Aminophosphonates are also suitable for use as chelating agents in compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylene diaminetetraquis (methylene phosphonates). [00116] Additional biodegradable scavengers are, for example, amino acid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Baypure CX. [00117] Preferably, the aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. [00118] A highly preferable biodegradable chelator for use here is ethylenediamine disuccinate ("EDDS"). [00119] If used, these selective transition metal chelating or sequestering agents in general will comprise from about 0.001% by weight to about 10% by weight, more preferably from about 0.05% by weight to about 1% by weight of dish washing detergent formulations, more preferably, automatic dish washing detergent formulations here. [00120] Preferred dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations here may additionally contain a dispersing polymer. When present, a dispersing polymer is typically at levels ranging from 0% by weight to about 25% by weight, preferably from about 0.5% by weight to about 20% by weight, more preferably from about 1 % by weight to about 8% by weight of the detergent composition. Dispersant polymers are useful for the improved film-forming performance of the present dishwashing detergent compositions, especially in Petition 870180071085, of 08/14/2018, p. 39/76 30/52 forms of high pH embodiments, such as those in which the pH of the wash exceeds about 9.5. Particularly preferred are polymers that inhibit the deposition of calcium carbonate or magnesium silicate in dishes. [00121] Suitable polymers are preferably at least partially neutralized ammonium salts or alkali metal, or substituted ammonium (e.g., mono-, di- or triethanolammonium) of polycarboxylic acids. Alkali metal, especially sodium salts are more preferred. While the molecular weight of the polymer can vary over a wide range, it is preferably about 1,000 to about 500,000, more preferably it is about 1,000 to about 250,000. [00122] Unsaturated monomeric acids that can be polymerized to form suitable dispersing polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenomalonic acid. The presence of monomeric segments not containing carboxylate roots such as methyl vinyl ether, styrene, ethylene, etc. it is suitable provided that such segments do not constitute more than about 50% by weight of the dispersing polymer. [00123] Acrylamide and acrylate copolymers having a molecular weight of about 3,000 to about 100,000, preferably from about 4,000 to about 20,000 and an acrylamide content of less than about 50% by weight, preferably less than about 20% by weight of the dispersing polymer can also be used. More preferably, such dispersing polymer has a molecular weight of about 4,000 to about 20,000 and an acrylamide content of about 0% by weight to about 15% by weight, based on the total weight of the polymer. [00124] Particularly preferred dispersing polymers are low molecular weight modified polyacrylate copolymers. Such copolymers contain as monomer units: a) about 90% by weight Petition 870180071085, of 08/14/2018, p. 40/76 31/52 weight at about 10% by weight, preferably from about 80% by weight to about 20% by weight of acrylic acid or its salts and b) from about 10% by weight to about 90% by weight, preferably from about 20% by weight to about 80% by weight of a substituted acrylic monomer or its salt and has the general formula: - [(C (R a ) C (R b ) (C (O) OR c ) ] where the seemingly unfilled valences are in fact occupied by hydrogen and at least one of the substituents Ra, Rb, or Rc, preferably Ra or Rb, is a 1 to 4 carbon alkyl or hydroxyalkyl group; R a or R b can be a hydrogen and Rc can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer in which Ra is methyl, Rb is hydrogen, and Rc is sodium. [00125] A low molecular weight polyacrylate dispersing polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, more preferably from about 1,000 to about 5,000. the most preferred polyacrylate copolymer for use therein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer comprising about 70% by weight of acrylic acid and about 30% by weight of methacrylic acid. [00126] Other dispersing polymers useful in this include polyethylene glycols and polypropylene glycols having a molecular weight of about 950 to about 30,000. [00127] Other dispersing polymers useful in these include cellulose sulfate esters such as cellulose sulfate acetate, cellulose sulfate, hydroxyethyl cellulose sulfate, methyl cellulose sulfate and hydroxypropyl cellulose sulfate. Sodium cellulose sulfate is the most preferred polymer in this group. [00128] Other suitable dispersing polymers are carboxylated polysaccharides, particularly starches, celluloses and alginates. Petition 870180071085, of 08/14/2018, p. 41/76 [00129] Another group of acceptable dispersants are organic dispersing polymers, such as polyaspartate. [00130] Depending on whether a greater or lesser degree of density is required, filler materials may also be present in immediate dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70% by weight, preferably from 0.1% by weight to about 40% by weight of detergent washing formulations. dish, more preferably automatic dishwashing detergent formulations. The preferred filler is sodium sulphate, especially in good grades having lower levels of trace impurities. [00131] The sodium sulfate used in this preferably is of sufficient purity to ensure it is not reactive with bleaching; it can also be treated with low levels of scavengers, such as phosphonates or EDDS in the form of magnesium salt. It is noted that the preferences, in terms of sufficient purity to prevent bleaching of the decomposition, also apply to the pH adjusting component ingredients, especially including any silicates used in it. [00132] Organic solvents that can be used in the cleaning formulations according to the invention, especially when the latter is in liquid or paste form, include alcohols having 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and mixtures of these and the ethers derived from the mentioned classes of the compound. Such water-miscible solvents are present in the cleaning formulations according to the invention, preferably in amounts not exceeding 20% by weight, especially in amounts of 1% by weight to 15% by weight. Petition 870180071085, of 08/14/2018, p. 42/76 33/52 [00133] Many dish washing detergent formulations, more preferably automatic dish washing detergent formulations in this will be buffered, that is, these are relatively resistant to the pH drop in the presence of acidic soils. However, other compositions in these can exceptionally have a low buffering capacity, or can be substantially non-buffered. Techniques for controlling or varying the pH at the recommended usage levels more generally include using not only buffers, but also additional alkalis, acids, pH jump systems, double compartment containers, etc. and are well known to that person skilled in the art. [00134] Certain dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations, comprise a pH adjustment component selected from the water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders. The pH adjustment components are selected so that when the dishwashing detergent formulation, more preferably automatic dishwashing detergent formulation is dissolved in water at a concentration of 1,000-5,000 ppm, the pH remains in the range above about from 8, preferably from about 9.5 to about 11. The preferred non-phosphate pH adjustment component can be selected from the group consisting of: (i) sodium carbonate or sesquicarbonate; (ii) sodium silicate, preferably water sodium silicate having a SiO2: Na2O ratio of about 1: 1 to about 2: 1, and mixtures thereof with limited amounts of sodium metasilicate; (iii) sodium citrate; (iv) citric acid; (v) sodium bicarbonate; (vi) sodium borate, preferably sodium borate; Petition 870180071085, of 08/14/2018, p. 43/76 34/52 (vii) sodium hydroxide; and (viii) mixtures of (i) - (vii). [00135] The preferred embodiments contain low levels of silicate (i.e. from about 3% by weight to about 10% by weight SiO 2 ). [00136] Illustrative of the highly preferred pH adjustment component systems of this specialized type are the binary mixtures of granular sodium citrate with anhydrous sodium carbonate and mixtures of three components of granular trihydrate sodium citrate, citric acid monohydrate and carbonate anhydrous sodium. [00137] The amount of the pH adjusting component in the compositions used for automatic dish washing is preferably from about 1% by weight to about 50% by weight of the composition. In a preferred embodiment, the pH adjusting component is present in the composition in an amount of about 5% by weight to about 40% by weight, preferably from about 10% by weight to about 30% by weight . [00138] For the compositions in this having a pH between about 9.5 and about 11 of the initial wash solution, particularly the embodiments of the preferred automatic disc washing detergent formulations comprise, by weight of the detergent wash detergent formulations automatic discs, from about 5% by weight to about 40% by weight, preferably from about 10% by weight to about 30% by weight, more preferably from about 15% by weight to about 20% by weight sodium citrate of about 5% by weight to about 30% by weight, preferably from about 7% by weight to 25% by weight, more preferably from about 8% by weight to about 20% by weight of sodium carbonate. [00139] The essential pH adjustment system can be complemented (that is, by improved sequestration in hard water) by other optional detergent builder salts selected from non-phosphate detergent builders known in the art, which includes the various ammonium borates soluble Petition 870180071085, of 08/14/2018, p. 44/76 35/52 in water, alkali metal, or substituted ammonium, hydroxysulfonates, polyacetates and polycarboxylates. Preferred are alkali metals, especially sodium, salts of such materials. Non-phosphorous, water-soluble organic builders can be used for their sequestering properties. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and ammonium salts substituted for ethylenediamine tetraacetic acid; nitrilotriacetic acid, monosuccinic tartrate acid, disuccinic tartrate acid, oxidisuccinic acid, carboxymethoxysuccinic acid, melitic acid and sodium benzene polycarboxylate salts. Additional biodegradable builders are, for example, amino acid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as derivatives of asparaginic acid, such as Baypure CX. [00140] Detergent formulations can take a variety of physical forms such as, for example, powder granules, tablets (tabs), gel and liquid. Examples of these include, inter alia, conventional high-performance post-detergents, super-compact high-performance post-detergents and tabs. An important physical form is the so-called concentrated granular form, which is added in a washing machine. [00141] Also of importance are detergents called compact or supercompact. In the field of detergent manufacturing, there is a direction close to the production of such detergents that contains an increased amount of the active substances. In order to minimize energy consumption during the washing procedure, compact or supercompact detergents needed to act effectively at low washing temperatures, for example, below 40 ° C, or at room temperature (25 ° C). Such detergents usually contain only minor amounts of fillers or substances, such as sodium sulfate or sodium chloride, required by detergent manufacturing. The total amount of such substances is usually 0 to 10% by weight, especially 0 to 5% Petition 870180071085, of 08/14/2018, p. 45/76 36/52 by weight, more especially from 0 to 1% by weight, based on the total weight of the detergent formulation. Such (super) compact detergents usually have a volume density of 650 to 1000 g / l, especially 700 to 1000 g / l and more especially 750 to 1000 g / l. [00142] Detergent formulations can also be in the form of tablets (tabs). The advantages of tabs lie in the case of dispersing and the convenience in handling. Tabs are the most compact form of the solid detergent formulation and usually have a volumetric density of, for example, 0.9 to 1.3 kg / liter. To achieve rapid dissolution, such tabs usually contain special dissolution aids: - carbonate / hydrogen carbonate / citric acid as effervescent; - disintegrators, such as cellulose, carboxymethyl cellulose or cross-linked polyvinylpyrrolidone; - Quickly dissolved materials, such as sodium acetates (potassium), or sodium citrates (potassium); - Rigid coating agents, soluble in water, quickly dissolved, such as dicarboxylic acids. [00143] Tabs can also comprise combinations of such dissolution aids. [00144] The detergent formulation can also be in the form of an aqueous liquid containing from 5% by weight to 50% by weight, preferably from 10% by weight to 35% by weight, of water or in the form of a non-liquid non-liquid containing more than 5% by weight, preferably from 0% by weight to 1% by weight of water. Aqueous non-liquid detergent formulations may comprise other solvents such as carriers. Primary or secondary low molecular weight alcohols, for example, methanol, ethanol, propanol and isopropanol, are suitable for that purpose. The solubilizing surfactant used is preferably a monohydroxy alcohol Petition 870180071085, of 08/14/2018, p. 46/76 37/52 but polyols, such as that containing 2 to 6 carbon atoms and 2 to 6 hydroxy groups (eg 1,3-propanediol, ethylene glycol, glycerol and 1,2-propanediol) can also be used. Such carriers are usually used in a total amount of 5% by weight to 90% by weight, preferably 10% by weight to 50% by weight, based on the total weight of the detergent formulation. Detergent formulations can also be used in the so-called “single liquid dosage” form. [00145] Also an aspect of the invention is a granule comprising a) from 1 to 99% by weight, based on the total weight of the granule, of at least one compound of formula (1) as described above and of at least one peroxide, b) from 1 to 99% by weight, based on the total weight of the granule, of at least one binder, (c) from 0 to 20% by weight, based on the total weight of the granule, of at least one encapsulating material, d) from 0 to 20% by weight, based on the total granule weight, of at least one additional additive, and e) 0 to 20% by weight based on the total weight of the granule, water. [00146] The granules according to the invention comprise a water-soluble organic polymer as a binder. Such polymers can be used simply or in the form of mixtures of two or more polymers. [00147] The water-soluble polymers that they take into account are, for example, polyethylene glycols, copolymers of ethylene oxide with propylene oxide, gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, polyvinylpyridine, polyvinylimidazole oxides, vinylpyrrolidone copolymers with long-chain olefins, vinylpyrrolidone copolymers with vinylimidazole, poly (vinylpyrrolidone / dimethylaminoethyl methacrylates), copolymers of Petition 870180071085, of 08/14/2018, p. 47/76 Methacrylamides 38/52 vinylpyrrolidone / dimetilaminopropila, acrylamides, copolymers of vinylpyrrolidone / dimetilaminopropila, quartenizados copolymers of vinylpyrrolidones dimetilaminoetila and methacrylates, terpolymers of methacrylates vinilcaprolactam / vinylpyrrolidone / dimetilaminoetila, copolymers of vinylpyrrolidone and methacrylamidopropyl-trimethylammonium chloride, terpolymers of methacrylates caprolactam / vinylpyrrolidone / dimethylaminoethyl, copolymers of styrene and acrylic acid, polycarboxylic acids, polyacrylamides, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinyl alcohols, polyvinyl acetate, hydrolyzed polyvinyl acetate, and copolymers of methyl acid and acrylates with acrylates maleic with unsaturated hydrocarbons and also the mixed polymerization products of the mentioned polymers. [00148] Of these organic polymers, special preference is given to polyethylene glycols, carboxymethyl cellulose, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolyzed polyvinyl acetates, vinylpyrrolidone copolymers and vinyl acetate and also polyacrylates and polyacrylates, copolymers and copolymers. and methacrylic acid and polymethacrylates. [00149] The encapsulating materials especially include polymers dispersible in water and soluble in water and waxes. Of these materials, preference is given to polyethylene glycols, polyamides, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolyzed polyvinyl acetates, vinylpyrrolidone copolymers and vinyl acetate and also polyacrylates, paraffins, fatty acids, and acrylates and acrylate copolymers. methacrylic acid and polymethacrylates. [00150] Additional additives (d) taken into account are, for example, wetting agents, dust removers, water-soluble or water-insoluble pigments or pigments and also accelerators of Petition 870180071085, of 08/14/2018, p. 48/76 39/52 dissolution, optical illuminators and sequestering agents. Examples have been readily given above. [00151] Another aspect of the invention is a process for bleaching stains or dirt on textile materials in the context of a washing process or by the direct application of a stain remover and for cleaning hard surfaces it comprises placing a textile material or a hard surface material in contact with an aqueous medium, a compound of formula (1) as described above and a peroxide or precursor to peroxide or O2 and / or air. [00152] Yet, another aspect of the invention is the use, as a catalyst for oxidation reactions, of at least one compound of the formula (1) the R í R í, Χ, 'νΛ / R < N r HO ' R 6 r 2 R 3 (1) where R1, R2, R3, R4 independently of one another are hydrogen, unsubstituted or substituted C1-C28 alkyl, C1-C28 alkoxy, C1-C28 alkenyl, C2-C22 alkynyl, C3-C12 cycloalkyl, C3-C12 cycloalkenyl, C7 aralkyl -C9, C3-C20 heteroalkyl, C1-C12 cycloetheroalkyl, C5-C16 heteroalkyl, unsubstituted or substituted phenyl or naphthyl, where the substituents for the radicals are selected from the group consisting of C1-C4 alkyl; C1-C4 alkoxy; hydroxy; sulfo; sulfate; halogen; cyan; nitro; carboxy; amino; N-mono- or N, N-di-C1-C4 amino substituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino in which the amino groups can be quaternized; phenyl; phenoxy or naphthyloxy; or R1, R2, R3, R4 independently of each other are OR11, NR 11 R 12 , NO 2 or halogen; or Petition 870180071085, of 08/14/2018, p. 49/76 40/52 Ri and R2, R2 and R3 or R3 and R4 are joined together to form 1, 2 or 3 carbocyclic or heterocyclic rings, which can be unbroken or interrupted by one or more -O-, -S- or -NR13- and / or that can still be fused with other aromatic rings and / or that can be replaced by one or more C1-C6 alkyl groups. R5 indicates hydrogen, unsubstituted or substituted C1-C28 alkyl, C1-C28 alkenyl, C2-C22 alkynyl, C3-C12 cycloalkyl, C3-C12 cycloalkenyl, C7-C9 aralkyl, C3-C20 heteroalkyl, C1-C12 cycloalkylalkyl, heteroalkyl -C16, unsubstituted or substituted phenyl or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C1-C4 alkyl; C1C4 alkoxy; hydroxy; sulfo; sulfate; halogen; cyan; nitro; carboxy; amino; N-mono N, N-di-C 1 -C 4 alkyl unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino in which the amino groups can be quaternized; phenyl; phenoxy or naphthyloxy; R6 indicates hydrogen, C1-C28 alkyl, C1-C28 alkenyl, C2-C22 alkynyl, C3-C12 cycloalkyl, C3-C12 cycloalkenyl, C7-C9 aralkyl, C3-C20 heteroalkyl, C1-C12 cycloethylalkyl, C5-C16 heteroalkyl, C5-C16 heteroalkyl unsubstituted or substituted or naphthyl or heteroaryl unsubstituted or substituted; wherein the substituents for the radicals are selected from the group consisting of C1-C4 alkyl; C1-C4 alkoxy; hydroxy; sulfo; sulfate; halogen; cyan; nitro; carboxy; amino; N-mono- or N, N-di-C1-C4 amino substituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino in which the amino groups can be quaternized; phenyl; phenoxy or naphthyloxy; R7 is a group rrrr R io R io R io R io - (CH 2 ) -NO (CH „) - NS - (CH„) - NI - (CH „) - NI k ^, k ^, k V 0 or k V ' S each group with an anion A - ; Petition 870180071085, of 08/14/2018, p. 50/76 41/52 k is an integer from 1 to 4; A - is an anion; R10 indicates hydrogen, C1-C28 alkyl, C1-C28 alkenyl, C2-C22 alkynyl, C3-C12 cycloalkyl, C3-C12 cycloalkenyl, C7-C9 aralkyl, C3-C20 heteroalkyl, C1-C12 cycloethylalkyl, C5-C16 heteroalkyl; R11, R12 are independently hydrogen, C1-C18 alkyl or phenyl; or R11 and R12 together with the nitrogen atom to which they are attached form a 5- or 6-membered ring that may still contain an N, O or S atom. R13 indicates hydrogen or C1-C18 alkyl. [00153] Preferably the compounds of formula (1) are used as catalysts together with peroxide or a peroxide precursor, O2 and / or air for bleaching stains or dirt on textile materials in the context of a washing process or by application direct from a stain remover; for cleaning hard surfaces. [00154] In a specific embodiment an additional bleach activator is used together with the compound of formula (1) and a peroxide or peroxide precursor, O2 and / or air. [00155] In another specific embodiment a metal chelating agent (scavenger) is used present together with the compound of the formula (1) and a peroxide or peroxide precursor, O2 and / or air. [00156] In many cases the bleach activator and the metallic chelating agent (scavenger) are used together with the compound of the formula (1) and a peroxide or a peroxide precursor, O2 and / or air. [00157] The definitions and preferences given above apply equally to all aspects of the invention. [00158] The following examples illustrate the invention. A) Examples of synthesis Example A1 Petition 870180071085, of 08/14/2018, p. 51/76 42/52 (compound 1A, precursor) Cl 0%. 0 O '[00159] Ethyl 2- (4-methylmorpholin-4-ium-4-yl) chloride: The title compound is synthesized as described in U.S. 3,398,147. [00160] 1 H-NMR (300MHz, DMSO), δ ppm: 1.25 (t, J = 7.2 Hz, 3H), 3.41 (s, 3H), 3.62-3.79 (m, 4H), 3.96-3.99 (m, 4H), 4.24 (q, J = 7.2 Hz, 2H) , 4.806 (s, 2H). Compound 101. r ν, α 0H 1 H [00161] N - [(2-hydroxyphenyl) methyleneamino] -2- (4methylmorpholin-4-ium-4-yl) acetamide chloride: 20.1 g (0.09 mol) of compound 1A are dissolved in 100 ml of ethanol. 9.1 g (0.18 mol) of hydrazine monohydrate are added to the drops at room temperature. A white suspension is obtained at the end of the addition and the reaction mixture is stirred at room temperature for 3 hours. The solid is then quickly filtered and dried. It is then further suspended in 100 ml of ethanol and 11.2 g (0.09 mol) of salicylaldehyde are added to the drops at room temperature. The reaction mixture is stirred at room temperature for 19 hours and is then filtered. The white solid obtained is dried to give 23.1 g of a mixture of two isomers of compound 101. 1 H-NMR (300MHz, DMSO), δ ppm: 3.45 (broad s, 3H), 3.60 - 3.87 (m, 4H), 3.93 - 4.07 (m, 4H), 4 , 63 and 4.95 (2 s, 1H), 6.83 - 7.02 (m, 2H), 7.23 -7.33 (m, 1H), 7.60 and 7.79 (2 dd, Ji = 1.5 Hz, J2 = 7.8 Hz and Ji = 1.8 Hz, J2 = 8.1 Hz, 1H), 8.42 and 8.64 (2s, 1H), 10.31 and 10, 85 (2s, 1H), 12.03 and 13.36 Petition 870180071085, of 08/14/2018, p. 52/76 43/52 (2s, 1H). Example A2 (compound 1B, precursor) Br O '0' [00162] Ethyl 2- (4-methylmorpholin-4-ium-4-yl) bromide: The title compound was synthesized as described in Koumoto, Kazuya; Ochiai, Hirofumi; Sugimoto, Naoki Tetrahedron 2007, 64, 168. [00163] 1 H-NMR (300MHz, DMSO), δ ppm: 1.25 (t, J = 7.2 Hz, 3H), 3.40 (s, 3H), 3.60-3.77 (m, 4H), 3.91-4.04 (m, 4H), 4.26 (q, J = 7.2 Hz, 2H) , 4.74 (s, 2H). (compound 1C, precursor) Br 1 H [00164] 2- (4-Methylmorpholin-4-ium-4-yl) acetohydrazide bromide 24.1 g (0.09 mol) of compound 1B are stirred with 100 ml of ethanol. 7.7 g (0.15 mol) of hydrazine monohydrate are added to the drops at room temperature. 5 minutes after the end of the addition, a white solid starts the precipitation. The reaction mixture is stirred at room temperature for 5 hours. The solid is then quickly filtered and dried to give 18.2 g of compound 1C. [00165] 1 H-NMR (300MHz, DMSO), δ ppm: 3.33 (s, 3H), 3.53-3.69 (m, 4H), 3.91 - 4.00 (m, 4H) , 4.21 (s, 2H), 4.54-4.63 (m, 2H), 9.78 (broad s, 1H). Compound 101B. Petition 870180071085, of 08/14/2018, p. 53/76 44/52 [00166] N - [(2-hydroxyphenyl) methyleneamino] -2- (4methylmorpholin-4-ium-4-yl) acetamide bromide: 17.8 g (0.07 mol) of compound 1C are stirred with 100 ml of ethanol. 8.7 g (0.07 mol) of salicylaldehyde were added to the drops at room temperature. A thick white suspension is obtained and is stirred at room temperature overnight. The solid is then filtered and dried to give 23.4 g of a white solid: a mixture of two isomers of compound 101B. [00167] Ή-NMR (300MHz, DMSO), δ ppm: 3.45 (s, 3H), 3.64 - 3.87 (m, 4H), 3.94 - 4.06 (m, 4H), 4.54 and 4.95 (2 s, 1H), 6.85 - 6.95 (m, 2H), 7.25 7.34 (m, 1H), 7.62 and 7.80 (2 dd, Λ = 1.5 Hz, J 2 = 7.8 Hz and Ji = 1.5 Hz, J 2 = 7.8 Hz, 1H), 8.39 and 8.56 (2s, 1H), 10.08 and 10.75 (broad 2s, 1H), 11.95 and 12.51 (broad 2s, 1H). [00168] Compound 102 ci Lit. prep. given compound 102 [00169] N- (2-hydroxy-1-naphthyl) methyleneamino] -2- (4methylmorpholin-4-ium-4-yl) acetamide: 2-hydroxynaphthaldehyde (98%; 5.08 g, 0 , 0289 mol) is added at 25 ° C in a stirred suspension of 2 (4-methylmorpholin-4-ium-4-yl) acetoidrazide chloride (5.77 g, 0.0275 mol; prepared according to US 3398147 ) in ethanol (50 ml) and the resulting suspension subsequently stirred at 25 ° C (overnight) and 50 ° C (one hour). The reaction mixture is filtered, the filter cake is resuspended in fresh ethanol (70 ml) and the resulting suspension is refluxed (one hour). Petition 870180071085, of 08/14/2018, p. 54/76 45/52 Filtration of heating (45 ° C) and drying of the filter cake yields the title compound (7.1 g). Yellow beige solid; Ή-NMR (400MHz, DMSO-d 6 ), δ ppm: 3.48 (s) and 3.50 (s; 3H), 3.65 - 3.88 (m, 4H), 3.97 - 4, 08 (m, 4H), 4.62 (s) and 5.03 (s; 2H), 7.25 - 7.27 (m, similar ad) and 7.31 - 7.33 (m, similar ad; 1H), 7.37 - 7.43 (m, 1H), 7.57 - 7.62 (m, 1H), 7.85 - 7.87 (m, similar to d), 7.89 - 7.91 (m, similar ad) and 7.94 - 7.96 (m, similar ad; 2H), 8.41 - 8.43 (m, similar ad) and 8.80 - 8.82 (m, similar ad; 1H), 8.96 (s) and 9.47 (s; 1H), 10.84 (broad s), 12.07 (broad s), 12.16 (broad s) and 13.54 (broad s; 2H); LC / MS (pos. ESI),% of area (m / z): observed 98.6 (328.2); calculated by C18H22N3O3: 328; [00170] Elemental analysis (Cl only): observed 9.4%; calculated by C18CIH22N3O3: 9.7%. Compound 103 cr 1 H Lit. prep. given compound 103 N- (2-hydroxy-5-nitro-phenyl) methyleneamino] -2- (4methylmorpholin-4-ium-4-yl) acetamide chloride: 2-Hydroxy-5-nitrobenzaldehyde (99%; 5.0 g, 0 , 0296 mol) is added at 25 ° C in a stirred suspension of 2- (4-methylmorpholin-4-ium-4-yl) acetoidrazide chloride (5.91 g, 0.0 282 mol; prepared according to US 3398147) in ethanol (50ml) and the resulting suspension subsequently stirred at 25 ° C (overnight) and 5 ° C (15 minutes). The reaction mixture is filtered and the filter cake dried to produce the title compound (9.9 g). Beige solid; Ή-NMR (400MHz, DMSO-d 6 ), δ ppm: 3.45 (s, 3H), 3.62 3.85 (m, 4H), 3.95 - 4.06 (m, 4H), 4 , 59 (s) and 5.01 (s; 2H), 7.21 (d, J = 9.1Hz) and 7.26 (d, J = 9.1Hz; 1H), 8.19 (dd, J = 9.1 and 2.9Hz, 1H), 8.42 (s), 8.57 (d, J = Petition 870180071085, of 08/14/2018, p. 55/76 46/52 2.9Hz), 8.59 (d, J = 2.9Hz) and 8.67 (s; 2H), 12.11 (broad s), 12.19 (broad s) and 13.26 (broad s; 2H); LC / MS (pos. ESI),% of the area (m / z): observed 99.0 (323.2); calculated by C14H19N4O5: 323; Elemental analysis (Cl only): observed 9.5%; calculated by C14CIH19N4O5: 9.9%. Compound 104 compound 104 Cl o A o, NH, Lit. prep. given [00171] N- (2-hydroxy-5-methoxy-phenyl) methyleneamino] -2- (4methylmorpholin-4-ium-4-yl) acetamide: 2-hydroxy-5-methoxybenzaldehyde (98%; 4, 74 g, 0.0305 mol) is added via the syringe within two minutes at 25 ° C in a stirred suspension of 2- (4-methylmorpholin4-ium-4-yl) acetoidrazide chloride (6.1 g, 0 , 0291 mol; prepared according to US 3398147) in ethanol (50 ml), resulting in the formation of a bulky precipitate. The reaction mixture is diluted with ethanol (20 ml) and subsequently stirred at 50 ° C (one hour) and 25 ° C (overnight). Filtration and drying of the filter cake yields the title compound (9.38 g). Yellowish solid; Ή-NMR (400MHz, DMSO-d 6 ), δ ppm: 3.44 (s, 3H), 3.61 3.62 (m, 1H), 3.69 - 3.74 (m, 2H), 3 , 72 (s) and 3.73 (s; 3H), 3.79 - 3.85 (m, 1H), 3.95 - 4.05 (m, 4H), 4.58 (broad s) and 4 , 95 (s; 2H), 6.88 - 6.94 (m, 2H), 7.15 7.16 (m, similar ad) and 7.305 - 7.310 (m, similar ad; 1H), 8.37 ( s) and 8.59 (s; 1H), 9.78 - 9.79 (m, similar to ad), 10.31 (s), 12.00 (s) and 13.08 13.13 (m, similar ad; 2H); LC / MS (pos. ESI),% of the area (m / z): observed 100.0 (308.2); calculated by C15H22N3O4: 308; Petition 870180071085, of 08/14/2018, p. 56/76 47/52 [00172] Elemental analysis (Cl only): observed 10.1%; calculated by C15CIH22N3O4: 10.3%. Compound 105 ci cr JÚL oY o no 2 OH 1 H 1 H Lit. prep. given compound 105 [00173] N- (2-hydroxy-3-nitro-phenyl) methyleneamino] -2- (4methylmorpholin-4-ium-4-yl) acetamide: 2-hydroxy-3-nitrobenzaldehyde (98%; 4.9 g, 0.0287 mol) is added at 25 ° C in a stirred suspension of 2- (4-methylmorpholin-4-ium-4-yl) acetohydrazide chloride (5.73 g, 0.0273 mol; prepared according to US 3398147) in ethanol (50 ml). The reaction mixture is conducted at 50 ° C, diluted with ethanol (20 ml), stirred for two hours at 50 ° C, cooled to 10 ° C and filtered. The filter cake is dissolved in reflux of methanol (400 ml), filtered and the clear hot filtrate allowed to cool. The resulting precipitate is separated and dried to produce the title compound (7.8 g). Yellow solid; Ή-NMR (400MHz, DMSO-d 6 ), δ ppm: 3.36 (broad s, 1H), 3.45 (s) and 3.46 (s; 3H), 3.62 - 3.68 (m , 1H), 3.70 - 3.76 (m, 2H), 3.80 - 3.86 (m, 1H), 3.95 - 4.05 (m, 4H), 4.66 (s) and 5.00 (s; 2H), 7.12 - 7.18 (m, similar to q, 1H), 7.97 - 8.00 (m, similar to d), 8.02 - 8.05 (m, similar ad), 8.07 - 8.09 (m, similar ad) and 8.20 - 8.22 (m, similar ad; 2H), 8.50 (s) and 8.74 (s; 1H), 12 , 29 (s, 1H); LC / MS (pos. ESI),% (m / z): observed 100.0 (323.2); calculated by C14H19N4O5: 323; [00174] Elemental analysis (Cl only): observed 9.0%; calculated by C14CIH19N4O5: 9.9%. [00175] Compound 107 (comparison). Petition 870180071085, of 08/14/2018, p. 57/76 48/52 α I 0 KA n / H Cl O N OH NH, Commercial Lit. prep. given [00176] [2 - [[((2-hydroxyphenyl) methylene] hydrazino] -2-oxoethyl] -trimethyl-ammonium chloride: from commercially available (2-hydrazino-2-oxo-ethyl) -trimethylammonium chloride (Girard-T reagent) and salicylaldehyde in ethanol according to a procedure published by V. Leovac et al., Structural Chemistry 2007,18, 113-119. B) Application examples (detergent containing phosphate) Application example Bi: (peroxide bleaching action on washing agents) g of white cotton fabric and 0.5 g each BC01, BC03 (tea macha), BC02 (coffee stain), CS 12 (currant stain) cotton) are treated in 250 ml of the washing liquid. The liquid substance contains standard detergent ECE77 (phosphate builder) in a concentration of 4.5 g / 1 and 0.92 g / l of sodium percarbonate (SPC), 0.176 mg of TAED, pH adjusted to pH 10.1. The catalyst concentration is 25 pmol / l. The washing process is carried out in a steel beaker in a LINITEST Apparatus for 60 minutes at 30 ° C. For the evaluation of the bleaching results, the increase in the DY clarity (difference in clarity according to the CIE) of the spots leads about by the treatment is determined spectrophotometrically. The higher the DY value, the better the bleaching performance. BC01 BC02 BC03 CS12 No catalyst 10.4 9.4 10.8 49 Reference ol k ^ NÇX N .N OH 1 H Compound 101A 15.5 12.9 18.3 51.1 Invention Petition 870180071085, of 08/14/2018, p. 58/76 49/52 HCCTCl107 11.9 9.8 14.2 49.5 Comparation [00177] The results clearly show that compound 101A according to the invention exhibits significantly greater clarity as compared to the reference compound. Odor of washing liquid substances [00178] After the washing experiment the washing liquid substance containing compound 101A has no aroma. The washing liquid substance containing comparative compound 107 exhibits a light fishy smell, which is highly undesirable. Application example B2: (peroxide bleaching, influence of scavengers) [00179] 50 g of white cotton fabric and 0.5 g each BC01, BC03 (tea stain), BC02 (coffee stain), CS12 (coffee stain) red currant) on the cotton fabric are treated in 250 ml of the washing liquid. The liquid substance contains AATCC standard detergent in a concentration of 4.5 g / l and 0.65 g / l of sodium percarbonate (SPC), 144 mg of TAED, pH adjusted to pH 10.1, tap water. The catalyst concentration is 35 pmol / l. The experiments are carried out with 1% of the active material by weight of the detergent of the different scavengers with and without the catalyst. The sequestrants used are: citric acid, oxalic acid, methyl-glycinadiacetic acid (MGDA), ethylenediamine-N, N'-disuccinic acid (EDDS), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). [00180] The washing process is carried out in a steel beaker in a LINITEST device for 60 minutes at 30 ° C. For the evaluation of the bleaching results, the increase in the Δ clar clarity (difference in clarity according to the CIE) of the spots leads about by the treatment is Petition 870180071085, of 08/14/2018, p. 59/76 50/52 determined spectrophotometrically. The higher the ΔΥ value, the better the bleaching performance. BC01 BC02 BC03 CS12 Reference TAED 9.0 7.7 8.7 44.3 + EDDS 8.0 6.9 6.9 42.9 + MGDA 8.4 7.3 7.8 42.9 + Oxalic acid 8.5 7 8.2 43.3 + citric acid 8.4 7.2 7.9 42.5 + HEDP 8.5 7.2 7.6 46.2 + Comp. 101A 13.2 9.5 14.6 43.5 + Comp. 101A + EDDS 15.2 11.6 18.2 49.2 + Comp. 101A + MGDA 15.2 10.7 18.7 47.9 + Comp. 101A + Oxalic acid 14.0 9.6 15.5 44.5 + Comp. 101A + Citric acid 14.9 10.3 17.0 46.5 + Comp. 101A + HEDP 15.1 11.3 17.7 47.6 [00181] The results clearly show a synergistic effect of the Comp combination. 101 + kidnapper. Application example B3: (peroxide bleaching, performance without TAED) g of white cotton fabric and 0.5 g each BC01, BC03 (tea stain), BC02 (coffee stain), CS12 (red currant stain) in cotton fabric are treated in 250 ml of the washing liquid substance. The liquid substance contains AATCC standard detergent in a concentration of 4.3 g / l and 0.43 g / l of sodium percarbonate (SPC), 43 mg of HEDP, pH 10.1, tap water. The concentration of Comp. 101 is varied from 7.5 - 25 μΜ. [00182] Reference 1 contains SPC only, Reference 2 contains SPC + 32 mg of TAED. [00183] The washing process is carried out in a steel beaker in a LINITEST device for 60 minutes at 40 ° C. For the evaluation of the bleaching results, the increase in the ΔΥ clarity (difference in clarity according to the CIE) of the spots leads about by the treatment is determined spectrophotometrically. The higher the ΔΥ value, the better the bleaching performance. Petition 870180071085, of 08/14/2018, p. 60/76 51/52 BC01 BC02 BC03 CS12 Ref. 1 - Det + SPC 9.1 5.9 9.2 43.3 Ref. 2 - Det + SPC + TAED 9.6 7.1 11.3 46.2 Det + SPC + 7.5 μΜ Comp. 101A 10.4 7.2 11.6 46.5 Det + SPC + 10 μΜ Comp. 101A 10.8 7.5 12.1 47.2 Det + SPC + 15 μΜ Comp. 101A 10.9 8.2 13.2 47.9 Det + SPC + 20 μΜ Comp. 101A 11.6 8.6 14.2 48.3 Det + SPC + 25 μΜ Comp. 101A 12.0 8.9 13.7 48.9 [00184] The results show that Comp. 101A catalyzes peroxide bleaching and is easily capable of exceeding the state of the bleaching system of the SPC / TAED technique. [00185] Application example B4, other compounds (peroxide bleaching, performance with TAED) g of white cotton fabric and 0.5 g each BC01, BC03 (tea stain), BC02 (coffee stain), CS12 (stain red currant) on the cotton fabric are treated in 250 ml of the washing liquid. The liquid substance contains AATCC standard detergent in a concentration of 4.7 g / l and 0.66 g / l of sodium percarbonate (SPC), 144 mg / l of TAED, 43 mg of HEDP, pH 10.1, tap water . The concentration of the different compound is 20 pmol / l. [00186] The reference contains SPC + TAED as a targeting system. [00187] The washing process is carried out in a steel beaker in a LINITEST device for 60 minutes at 30 ° C. For the evaluation of the bleaching results, the increase in the ΔΥ clarity (difference in clarity according to the CIE) of the spots leads about by the treatment is determined spectrophotometrically. The higher the ΔΥ value, the better the bleaching performance. BC01 BC02 BC03 CS12 Reference 8.5 6.9 9.0 46.0 Reference + Comp. 102 12.1 8.8 15.1 47.0 Reference + Comp. 103 10.2 7.5 10.6 47.1 Reference + Comp. 104 10.0 7.1 10.1 45.9 Reference + Comp. 105 9.6 7.0 10.6 48.2 Application example B5, other compounds (peroxide bleaching, performance without TAED) g of white cotton fabric and 0.5 g each BC01, BC03 Petition 870180071085, of 08/14/2018, p. 61/76 52/52 (tea stain), BC02 (coffee stain), CS12 (red currant stain) on the cotton fabric are treated in 250 ml of the washing liquid. The liquid substance contains EU-based detergent in a concentration of 4.7 g / l and 0.66 g / l of sodium percarbonate (SPC), 43 mg of HEDP, pH 10.2, tap water. The concentration of the different compound is 20 pmol / l. [00188] The reference contains SPC as a targeting system. [00189] The washing process is carried out in a steel beaker in a LINITEST device for 60 minutes at 40 ° C. For the evaluation of the bleaching results, the increase in the ΔΥ clarity (difference in clarity according to the CIE) of the spots leads about by the treatment is determined spectrophotometrically. The higher the ΔΥ value, the better the bleaching performance. BC01 BC02 BC03 CS12 Reference 8.1 6.1 8.2 43.4 Reference + Comp. 102 11.7 8.9 15.4 47.8 Reference + Comp. 104 10.7 7.8 12.8 46.1 Petition 870180071085, of 08/14/2018, p. 62/76
权利要求:
Claims (12) [1] 1. Composition, characterized by the fact that it comprises a) H2O2 or a precursor to H2O2 and b) a compound of formula (1) R R i Λ- * N R. H0 R Rq R (1) where R1, R2, R3, R4 independently of one another are hydrogen, C1-C6 alkyl, C1-C6 alkoxy, NO2; or R1 and R2, R2 and R3 or R3 and R4 are joined together to form a carbocyclic ring; R5 indicates hydrogen or C1-C6 alkyl; R6 indicates hydrogen or C1-C6 alkyl; R 7 is a group FR n R '10 - (CH „) - N + o 2 k - / - (CH 2 ) -N or each group with an A anion - of an organic or inorganic acid; k is an integer from 1 to 2; R10 indicates hydrogen or C1-C6 alkyl. [2] 2. Composition according to claim 1, characterized by the fact that in formula (1) R1, R2, R3, R4 independently of one another are hydrogen, methoxy, NO2 or methyl; or R1 and R2, R2 and R3 or R3 and R4 are linked together to form a condensed phenyl ring; Petition 870190000476, of 01/03/2019, p. 9/12 2/4 R 5 indicates hydrogen or methyl; Ró indicates hydrogen or methyl; R 7 is a group R 10 t - (CH „) - N + O κ - / with an anion A - ; k is an integer from 1 to 2; A - is Cl - , Br - , ClO4 - , NO3 - , HSO4-, BF4 - or PFó - ; Rio indicates hydrogen or C 1 -C 4 alkyl. [3] 3. Composition according to claim 1 or 2, characterized by the fact that in formula (1) R 5 indicates hydrogen; Ró indicates hydrogen; R 7 is a group R 10 t - (CH „) - N + O κ - / with an anion A - ; k is 1; A - is Cl - or Br - ; R 10 indicates methyl. [4] Composition according to any one of claims 1 to 3, characterized by the fact that an additional bleach activator is present. [5] Composition according to any one of claims 1 to 4, characterized in that, in addition, a metal chelating agent (scavenger) is present. [6] 6. Detergent, cleaning composition, disinfectant or bleach, characterized by the fact that it comprises I) from 0 to 50% by weight, based on the total weight of the composition, A) Petition 870190000476, of 01/03/2019, p. 12/10 3/4 of at least one anionic surfactant and / or B) of a nonionic surfactant, II) from 0 to 70% by weight, based on the total weight of the composition, C) at least one forming substance, III) from 1 to 99% by weight, based on the total weight of the composition, D) at least one peroxide and / or a peroxide-forming substance, O2 and / or air, IV) E) at least one compound of the formula (1) as defined in any one of claims 1 to 3 in an amount which, in the liquid, gives a concentration of 0.5 to 100 mg / liter of liquid, when 0, 5 to 50 g / liter of detergent, cleaning agent, disinfectant or bleach are added to the liquid, V) from 0 to 20% by weight, based on the total weight of the composition, of at least one additional additive and VI) water ad 100% by weight, based on the total weight of the composition. [7] 7. Granule, characterized by the fact that it comprises a) from 1 to 99% by weight, based on the total weight of the granule, of at least one compound of the formula (1) as defined in any one of claims 1 to 3 and of at least one peroxide, b) from 1 to 99% by weight, based on the total weight of the granule, of at least one binder, (c) from 0 to 20% by weight, based on the total weight of the granule, of at least one encapsulating material, d) from 0 to 20% by weight, based on the total granule weight, of at least one additional additive, and e) 0 to 20% by weight based on the total weight of the granule, water. [8] 8. Process for bleaching stains or dirt on textile materials in the context of a washing process or by the direct application of a stain remover and for cleaning hard surfaces, Petition 870190000476, of 01/03/2019, p. 12/11 4/4 characterized by the fact that it comprises placing a textile material or a hard surface material in contact with an aqueous medium, a compound of formula (1) as defined in any one of claims 1 to 3 and H 2 O 2 or a precursor to H2O2 or O2 and / or air. [9] 9. Use of at least one compound of the formula (1) as defined in claim 1, characterized by the fact that it is as a catalyst for oxidation reactions. [10] 10. Use according to claim 9, characterized by the fact that the compounds of formula (1) are used as catalysts together with peroxide or a precursor to peroxide, O2 and / or air for bleaching stains or dirt on materials textiles in the context of a washing process or by the direct application of a stain remover or for cleaning hard surfaces. [11] 11. Use according to claim 10, characterized by the fact that an additional bleach activator is present. [12] Use according to claim 10 or 11, characterized by the fact that, in addition, a metal chelating agent (scavenger) is present.
类似技术:
公开号 | 公开日 | 专利标题 BR112013014591B1|2019-04-16|COMPOSITION, DETERGENT, CLEANING, DISINFECTANT OR BLASTING COMPOSITION, GRANULA, PROCESS FOR STAINING DIRT OR DIRT IN MATERIALS, AND USE OF COMPOUND ES2651319T3|2018-01-25|Metal free bleaching composition ES2727511T3|2019-10-16|Use of hydrazide compounds as oxidation catalysts JP5270678B2|2013-08-21|Use of metal complex compounds as oxidation catalysts WO2017076771A1|2017-05-11|Bleach catalysts EP3372663A1|2018-09-12|Bleach catalysts EP3176157A1|2017-06-07|Bleach catalysts WO2017186480A1|2017-11-02|Metal free bleaching composition
同族专利:
公开号 | 公开日 US20160136627A1|2016-05-19| BR112013014591A2|2016-07-19| RU2013132311A|2015-01-20| US9533296B2|2017-01-03| EP2805942B1|2016-03-16| AU2011344415A1|2013-07-04| JP6081640B2|2017-02-15| JP2016166226A|2016-09-15| EP2805942A1|2014-11-26| WO2012080088A1|2012-06-21| JP2014501230A|2014-01-20| US9296713B2|2016-03-29| ES2524734T3|2014-12-11| PL2805942T3|2016-09-30| ES2576504T3|2016-07-07| MX2013006378A|2013-08-15| CN103328455A|2013-09-25| AU2011344415B2|2016-05-26| EP2651907B1|2014-10-01| RU2578565C2|2016-03-27| CN103328455B|2016-02-24| KR20140031853A|2014-03-13| US20130261041A1|2013-10-03| US9051285B2|2015-06-09| US20150225357A1|2015-08-13| KR101912962B1|2018-10-29| EP2651907A1|2013-10-23| PL2651907T3|2015-03-31| JP5923109B2|2016-05-24|
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法律状态:
2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: B01J 31/02 (2006.01), B01J 31/18 (2006.01), B08B 3 | 2018-05-15| B15K| Others concerning applications: alteration of classification|Ipc: C07D 295/15 (2006.01), B01J 31/18 (2006.01), C11D | 2018-05-22| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]| 2018-10-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]| 2019-02-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]| 2019-04-16| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/12/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/12/2011, OBSERVADAS AS CONDICOES LEGAIS | 2020-12-22| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. | 2021-04-13| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2607 DE 22-12-2020 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |
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申请号 | 申请日 | 专利标题 US42225110P| true| 2010-12-13|2010-12-13| EP10194758.8|2010-12-13| US61/422251|2010-12-13| EP10194758|2010-12-13| PCT/EP2011/072238|WO2012080088A1|2010-12-13|2011-12-08|Bleach catalysts| 相关专利
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