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Title:
BLEACH CATALYSTS
Document Type and Number:
WIPO Patent Application WO/2017/076771
Kind Code:
A1
Abstract:
The present invention relates to selected acylhydrazone compounds, their use as oxidation catalysts and to a process for removing stains and soil on textiles and hard surfaces. The compounds contain two acylhydrazone groups per molecule which are bonded together via a linking group. Further aspects of the invention are compositions or formulations comprising such compounds.

Inventors:
FREY MARKUS (CH)
ROHWER HAUKE (DE)
KOHLI STECK RACHEL (CH)
Application Number:
PCT/EP2016/076096
Publication Date:
May 11, 2017
Filing Date:
October 28, 2016
Export Citation:
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Assignee:
BASF SE (DE)
International Classes:
C07D295/15; B01J31/02; C07C251/86; C11D3/28; C11D3/30; D06L4/70
Domestic Patent References:
WO2009124855A12009-10-15
WO2012080088A12012-06-21
WO2009124855A12009-10-15
WO2012080088A12012-06-21
WO1995007972A11995-03-23
WO1996040661A11996-12-19
WO2004007657A12004-01-22
WO1992011347A21992-07-09
WO1994023005A11994-10-13
WO1994002597A11994-02-03
WO2002002865A22002-01-10
WO2004005688A12004-01-15
Foreign References:
JPS51143012A1976-12-09
DE19639603A11998-04-02
GB836988A1960-06-09
GB864798A1961-04-06
GB907356A1962-10-03
GB1003310A1965-09-02
GB1519351A1978-07-26
DE3337921A11985-05-02
EP0185522A21986-06-25
EP0174132A21986-03-12
EP0120591A11984-10-03
US1246339A1917-11-13
US3332882A1967-07-25
US4128494A1978-12-05
US4412934A1983-11-01
US4675393A1987-06-23
DE4443177A11996-06-13
US4751015A1988-06-14
US4397757A1983-08-09
EP0284292A21988-09-28
EP0331229A21989-09-06
EP0303520A21989-02-15
EP0458396A11991-11-27
EP0790244A11997-08-20
EP0464880A11992-01-08
EP1194514A12002-04-10
EP1383857A22004-01-28
US6242405B12001-06-05
Other References:
C. MITCHINSON: "Oxidatively Resistant alpha-Amylases", 207TH AMERICAN CHEMICAL SOCIETY NATIONAL MEETING, 13 March 1994 (1994-03-13)
Z. DEGA-SZAFRAN ET AL., JOURNAL OF MOLECULAR STRUCTURE, vol. 614, 2002, pages 23 - 32
N. SUGIMOTO ET AL., TETRAHEDRON, vol. 64, 2008, pages 168 - 174
R. C. DUTY ET AL., J. ORG. CHEM., vol. 35, no. 6, 1970, pages 1800 - 1802
Attorney, Agent or Firm:
BASF IP ASSOCIATION (ZRX - C6, Ludwigshafen, DE)
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Claims:
Claims

1. A compound of formula (1 a) or (1 b)

wherein in formula (1 a)

Q is Ci-C4alkylene

R1, R2, R3 and R4 independently from each other are Ci-Cisalkyl

or Q, R1 and R3 together with the nitrogen atoms to which they are bonded form a 5, 6 or 7 membered heterocyclic ring system;

R5, R6, R9 and R10 are hydrogen or Ci-Ci8alkyl;

R7, R8, R11 and R12 are independently hydrogen, Ci-Ciealkyl, Ci-Ciealkoxy, halogen or N02;

k is an integer from 1 to 8, preferably from 1 to 4;

X- and Y- are the same or different and are the anions of an inorganic or organic acid; wherein in formula (1 b)

R1 and R2 independently from each other are Ci-Cisalkyl or together with the nitrogen atom to which they are bonded form a heterocyclic 5, 6 or 7 membered ring system which may contain an additional N or O atom;

and the other definitions are the same as defined in formula (1 a).

2. A compound of formula (1 a) or (1 b) according to claim 1

wherein in formula (1 a)

Q is C2-C3alkylene

R1, R2, R3 and R4 independently from each other are d-Csalkyl

or Q, R1 and R3 together with the nitrogen atoms to which they are bonded form a 6 or 7 membered heterocyclic ring system;

R5, R6, R9 and R10 are hydrogen or Ci-C8alkyl;

R7, R8, R11 and R12 are independently hydrogen or Ci-C8alkyl;

k is an integer from 1 to 4;

X- and Y- are the same or different and are S03", Ch, Br, CIO4-, NO3-, HSO4-, BF4- or PF6-; wherein in formula (1 b)

R1 and R2 independently from each other are d-Csalkyl or together with the nitrogen atom to which they are bonded form a heterocyclic 6 or 7 membered ring system which may contain an additional N or O atom;

and the other definitions are the same as defined in formula (1 a). 3. A compound of formula (1 a) or (1 b) according to claim 1 or 2

wherein in formula (1 a)

Q is C2-C3alkylene

R1, R2, R3 and R4 independently from each other are Ci-C4alkyl or

Q, R1 and R3 together with the nitrogen atoms to which they are bonded form a 6 mem- bered heterocyclic ring system;

R5, R6, R9 and R10 are hydrogen or Ci-C4alkyl;

R7, R8, R11 and R12 are independently hydrogen or Ci-C4alkyl;

k is an integer from 1 to 2;

X- and Y- are the same or different and are SO3-, CI-, Br-, CI04-, NO3-, HS04-, BF4- or PF6-; wherein in formula (1 b)

R1 and R2 independently from each other are Ci-C4alkyl or together with the nitrogen atom to which they are bonded form a heterocyclic 6 membered ring system which may contain an additional N or O atom;

and the other definitions are the same as defined in formula (1 a).

4. A compound of formula (1 a) or (1 b) according to any preceding claim which is N O H

H N'

compound 101

compound 102 "

compound 103

5. A composition comprising

a) H2O2 or a precursor of H2O2; and

b) a compound of formula (1 a) or (1 b) according to claim 1 to 4. 6. A composition according to claim 5 wherein an additional bleach activator is present.

7. A composition according to claim 5 or 6 wherein additionally a metal chelating agent (sequestrant) is present. 8. A detergent, cleaning, disinfecting or bleaching composition comprising I) from 0 to 50 wt-%, based on the total weight of the composition, A) of at least one anionic surfactant and/or B) of a non-ionic surfactant,

II) from 0 to 70 wt-%, based on the total weight of the composition, C) of at least one builder substance,

III) from 1 - 99 wt-%, based on the total weight of the composition, D) of at least one peroxide and/or one peroxide-forming substance, O2 and/or air,

IV) E) at least one compound of formula (1 a) or (1 b) according to claim 1 to 4 in an amount that, in the liquor, gives a concentration of from 0.5 to 100 mg/litre of liquor, when from 0.5 to 50 g/litre of the detergent, cleaning, disinfecting or bleaching agent are added to the liquor,

V) from 0 - 20 wt-%, based on the total weight of the composition, of at least one further additive, and

VI) water ad 100 wt-%, based on the total weight of the composition. 9. A granule comprising

f) from 1 - 99 wt-%, based on the total weight of the granule, of at least one compound of formula (1 a) or (1 b) according to claim 1 to 4 and of at least one peroxide,

g) from 1 - 99 wt-%, based on the total weight of the granule, of at least one binder, h) from 0 - 20 wt-%, based on the total weight of the granule, of at least one encapsulating material,

i) from 0 - 20 wt-%, based on the total weight of the granule, of at least one further additive and

j) from 0 - 20 wt-% based on the total weight of the granule, of water. 10. A coated granulate comprising

a) a core pellet comprising

5 to 40% by weight based on the weight of the total granule of an acylhydrazone of formula (1 a) or (1 b) according to claim 1 to 4 and

1 % to 10% by weight based on the weight of the total granule of water and/or a water solu- ble polymer binder which is selected from the group consisting of polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, cellulose derivatives, carbohydrates, polyethyleneglycols and mixtures thereof; b) 0.1 % to 25% by weight based on the weight of the total granule of a subcoating compris- ing a polymer mixture of hydroxypropylmethylcellulose (HPMC) and methylcelluolose (MC) in a ratio by weight of from 2:1 to 8:1 ; c) optionally 1 % to 20% by weight based on the weight of the total granule of a topcoating comprising a fatty acid selected from nonadecanoic acid, stearic acid, palmitic acid, myristic acid and mixtures thereof; and d) other ingredients the sum of components a) to d) adding to 100%.

11. A process for the bleaching of stains or of soiling on textile materials in the context of a washing process or by the direct application of a stain remover and for the cleaning of hard surfaces comprising

bringing into contact a textile material or a hard surface material in an aqueous medium, a compound of formula (1 a) or (1 b) according to claim 1 to 4 and H2O2 or a precursor of H2O2

12. Use, as a catalyst for oxidation reactions, of at least one compound of formula (1 a) or (1 b)

wherein in formula (1 a)

Q is Ci-C4alkylene

R1, R2, R3 and R4 independently from each other are Ci-Cisalkyl

or Q, R1 and R3 together with the nitrogen atoms to which they are bonded form a 5, 6 or 7 membered heterocyclic ring system;

R5, R6, R9 and R10 are hydrogen or Ci-Ci8alkyl;

R7, R8, R11 and R12 are independently hydrogen, Ci-Cisalkyl, Ci-Cisalkoxy, halogen or N02;

k is an integer from 1 to 8, preferably from 1 to 4; X- and Y- are the same or different and are the anions of an inorganic or organic acid; wherein in formula (1 b)

R1 and R2 independently from each other are Ci-Ciealkyl or together with the nitrogen at- om to which they are bonded form a heterocyclic 5, 6 or 7 membered ring system which may contain an additional N or O atom;

and the other definitions are the same as defined in formula (1 a).

13. Use according to claim 12 wherein the compounds of formula (1 a) or (1 b) are used as catalysts together with peroxide or a peroxide-precursor, O2 and/or air for the bleaching of stains or of soiling on textile materials in the context of a washing process or by the direct application of a stain remover or for the cleaning of hard surfaces.

14. Use according to claim 13 wherein an additional bleach activator is present.

15. Use according to claim 13 or 14 wherein additionally a metal chelating agent (sequestra nt) is present.

Description:
Bleach Catalysts Description The present invention relates to selected acylhydrazone compounds, their use as oxidation catalysts and to a process for removing stains and soil on textiles and hard surfaces. The compounds contain two acylhydrazone groups per molecule which are bonded together via a linking group. Further aspects of the invention are compositions or formulations comprising such compounds.

Metal complex catalysts with hydrazide ligands have in generally been described as oxidation catalysts, for example, in DE 196 39 603. However, the compounds disclosed are not active enough. In WO 2009/124855 metal complex compounds having hydrazide ligands, preferably with electron withdrawing groups adjacent to the acyl group are described. The respective acylhydrazone ligands and their use are also described.

In WO 2012/080088 compounds are disclosed which differ from those described in WO 2009/124855 by being substituted with a specific cyclic ammonium group adjacent to the acyl group. This specific substitution pattern ensures a significantly higher bleaching activity as compared to prior art complexes or ligands.

The instant compounds differ from those of WO 2009/124855 and WO 2012/080088. The instant compounds contain two acylhydrazone groups per molecule which are bonded together via a linking group. The compounds are used especially for enhancing the action of H2O2 or peroxides, for example, in the treatment of textile materials, without at the same time causing any appreciable damage to fibres and dyeings. The instant compounds may also be used as catalysts for oxidation using molecular oxygen and/or air, that is, without peroxide compounds and/or peroxide-forming substances. The bleaching of the fabric can happen during and/or after the treatment of the fibre with the formulation, which comprises the compounds. Their stability in detergent formulations is high.

Metal ions, such as aluminium, zink, manganese, titanium, iron, cobalt, nickel or copper, for example Al(lll), Zn(ll), Mn(ll)-(III)-(IV)-(V), Cu(l)-(ll)-(lll), Fe(l)-(II)-(III)-(IV), Co(l)-(ll)-(lll), Ni(l)-(ll)-(lll), Ti(ll)-(III)-(IV) or for instance Mn(ll)-(III)-(IV)-(V), Cu(l)-(ll)-(lll), Fe(l)-(ll)-(lll)- (IV) and Co(l)-(ll)-(lll) may be present during the treating process of textile materials but are not necessary for the improved bleaching effect.

Peroxide-containing bleaching agents have long been used in washing and cleaning processes. They have an excellent action at a liquor temperature of 90°C and above, but their performance noticeably decreases with 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 manner it is possible for the bleaching effect, which is unsatisfactory at lower temperatures, of H2O2 or precursors that release H2O2 and of other peroxo compounds, to be increased.

The aim of the present invention is accordingly to provide improved metal free catalysts for oxidation processes that meet the above requirements and, especially, enhance the action of peroxide compounds in the most varied fields of application without causing any appre- ciable damage.

Bleaching activity should exceed the activity of prior art compounds.

One aspect of the invention is a compound of formula (1 a) or (1 b)

(1 a)

wherein in formula (1 a)

Q is Ci-C4alkylene

R 1 , R 2 , R 3 and R 4 independently from each other are Ci-Cisalkyl or

Q, R 1 and R 3 together with the nitrogen atoms to which they are bonded form a 5, 6 or 7 membered heterocyclic ring system;

R 5 , R 6 , R 9 and R 10 are hydrogen or Ci-Ci 8 alkyl;

R 7 , R 8 , R 11 and R 12 are independently hydrogen, Ci-Cisalkyl, Ci-Cisalkoxy, halogen or N0 2 ;

k is an integer from 1 to 8, preferably from 1 to 4;

X- and Y- are the same or different and are the anions of an inorganic or organic acid; wherein in formula (1 b)

R 1 and R 2 independently from each other are Ci-Ciealkyl or together with the nitrogen atom to which they are bonded form a heterocyclic 5, 6 or 7 membered ring system which may contain an additional N or O atom;

and the other definitions are the same as defined in formula (1 a).

Where applicable the acyl hydrazone derivatives can be in their E- or Z-configuration. When R 5 or R 9 are hydrogen the compound of formula (1 a) or (1 b) may be in one of its tautomeric forms or as a mixture of its different tautomeric forms. The compounds of formula (1 a) and (1 b) may also be ligands in metal complexes, such as Mn(ll)-(III)-(IV)-(V), Cu(l)-(ll)-(lll), Fe(l)-(II)-(III)-(IV), Co(l)-(ll)-(lll). 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.

The inorganic or organic anion X- and Y- may be an anion such as RCOO-, CI0 4 -, BF4-, PF6" , RSO3-, RSO4-, S0 4 2 -, H2PO4-, HPO4 2 -, OCN-, SCN-, NO3-, F-, CI-, Br- or HCOr, with R be- ing hydrogen, optionally substituted Ci-C24alkyl or optionally substituted aryl. Examples are lactic acid, citric acid, tartaric acid, succinic acid.

For anions with a charge greater than -1 the charge balance is established by additional cations, such as H + , Na + , K + , NH 4 + .

For example X- and Y- are RCOO, CI0 4 -, BF 4 -, PF 6 -, RSO3-, RS0 4 " , S0 4 2" , NO3-, F-, Ch, Br and I- wherein R is linear or branched Ci-Cisalkyl or phenyl. Cyclic substituents are preferably 5-, 6- or 7-membered rings, 6-membered rings are preferred.

The Ci-Cisalkyl radicals mentioned for the compounds of formula (1 a) and (1 b) are, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopro- pyl, n-butyl, sec-butyl, isobutyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl. Preference is given to Ci-Ci2alkyl radicals, especially d-Csalkyl radicals and preferably Ci-C 4 alkyl radicals. Very special preference is given to methyl and ethyl, especially methyl.

In the compounds of formulae (1 a) and (1 b) halogen is preferably chlorine, bromine or fluo- rine, with special preference being given to chlorine.

For example the compound of formula (1 a) or (1 b) in formula (1 a)

Q is C2-C3alkylene

R 1 , R 2 , R 3 and R 4 independently from each other are d-Csalkyl or

Q, R 1 and R 3 together with the nitrogen atoms to which they are bonded form a 6 or 7 membered heterocyclic ring system;

R 5 , R 6 , R 9 and R 10 are hydrogen or Ci-C 8 alkyl;

R 7 , R 8 , R 11 and R 12 are independently hydrogen or Ci-C 8 alkyl;

k is an integer from 1 to 4;

X- and Y- are the same or different and are SO3 , Ch, Br, CI0 4 -, NO3-, HS0 4 -, BF 4 - or PF 6 -; in formula (1 b)

R 1 and R 2 independently from each other are d-Cealkyl or together with the nitrogen atom to which they are bonded form a heterocyclic 6 or 7 membered ring system which may con- tain an additional N or O atom;

and the other definitions are the same as defined in formula (1 a).

For instance the compound of formula (1 a) or (1 b) in formula (1 a)

Q is C2-C3alkylene

R 1 , R 2 , R 3 and R 4 independently from each other are Ci-C 4 alkyl or

Q, R 1 and R 3 together with the nitrogen atoms to which they are bonded form a 6 membered heterocyclic ring system;

R5, R 6 , R9 and R 10 are hydrogen or Ci-C alkyl;

R 7 , R 8 , R 11 and R 12 are independently hydrogen or Ci-C 4 alkyl; k is an integer from 1 to 2;

X- and Y- are the same or different and are S0 3 " , Ch, Br, CIO4-, NO3-, HSO4-, BF 4 - or PF 6 -; in formula (1 b)

R 1 and R 2 independently from each other are Ci-C 4 alkyl or together with the nitrogen atom to which they are bonded form a heterocyclic 6 membered ring system which may contain an additional N or O atom;

and the other definitions are the same as defined in formula (1 a). In a specific la (1 a) or (1 b) is

pound 101

compound 102

Br "

The compounds can be prepared according to standard procedures by reacting a carbonyl compound, such as an aldehyde with a primary amine to form the corresponding Schiff base, in particular with a hydrazide and with a carbonyl compound wherein the substituents are as defined above. The compounds may be, for example, prepared in analogy to those described in WO 2009/124855 or WO 2012/080088.

The compounds of formula (1 a) and (1 b) including the above described preferences are novel compounds. The compounds of formula (1 a) and (1 b) are useful as catalysts for oxidation reactions, for the bleaching of stains and soil on textiles or for the cleaning of hard surfaces.

Therefore, another aspect of the invention is a composition comprising

a) H2O2 or a precursor of H2O2; and

b) a compound of formula (1 a) or (1 b) as described above.

The amount of component b), compound of formula (1 a) or(1 b), in the composition may vary from 0.00001 weight-% to 1 weight-%, preferably from 0.0001 weight-% to 0.1 weight- %, based on the weight of the total composition.

In many cases in the composition as described above additional bleach activator is present. Suitable bleach activators are outlined below.

The amount of bleach activator in the composition may vary from 0.1 weight-% to 12 weight-%, preferably from 0.5 weight-% to 10 weight-%, based on the weight of the total composition.

It may be of advantage when the composition as described above optionally contains one or more metal chelating agents (sequestrants), such as hydroxyethyldiphosphonate (HEDP). More generally, chelating agents suitable for use herein can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Other suitable chelating agents for use herein are the commercial DEQUEST series, and chelants from Nalco, Inc.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetrace- tates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof. 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 ethylenediaminetetrakis (methylenephosphonates). Further biodegradable sequestrants are, for example, aminoacid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Bay pure CX. Preferably, the aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

A highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS").

Preferred are the following chelating agents (sequestrants): Citric acid, Oxalic acid, methyl- glycine-diacetic acid (MGDA), ethylenediamine-N,N'-disuccinic acid (EDDS), 1-hydroxy ethylidene-1 ,1-diphosphonic acid (HEDP). If utilized, these chelating agents or transition-metal selective sequestrants will generally be present from about 0.001 weight-% to about 10 weight-%, more preferably from about 0.05 weight-% to about 1 weight-%, based on the weight of the total compositionn.

Component a) of the composition may be H2O2, a precursor of H2O2 or a peroxide forming substance. Preferred are precursors of H2O2, such as peroxides or peracids outlined below.

As precursors of H2O2 peroxides come into consideration. I. e. every compound which is capable of yielding hydrogen peroxide in aqueous solutions, for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95°C.

Preferably, however, inorganic peroxides are used, for example persulfates, perborates, percarbonates and/or persilicates. They are typically used in an amount of 2-80 wt-%, preferably of 4-30 wt-%, based on the weight of the composition.

Typically the compound of formula (1 a) or (1 b) is present in the composition in an amount of 0.05-15 wt-%, preferably from 0.1 to 10 wt-%, based on the weight of the total composition. Examples of suitable inorganic peroxides are sodium perborate tetrahydrate or sodium perborate monohydrate, sodium percarbonate, inorganic peroxyacid compounds, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-80 wt-%, preferably from 4-30 wt-%, based on the weight of the composition.

The organic peroxides are, for example, mono- or poly-peroxides, urea peroxides, a combination of a Ci-C4alkanol oxidase and Ci-C4alkanol (Such as methanol oxidase and etha- nol as described in WO95/07972), alkylhydroxy peroxides, such as cumene hydroperoxide and t-butyl hydroperoxide.

The peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.

As oxidants, peroxo acids can also be used. One example are organic mono peracids of formula 9

Ri g - C-O-OM

wherein

M signifies hydrogen or a cation,

Rig signifies unsubstituted C-i-dsalkyl; substituted C-i-dsalkyl; unsubstituted aryl; substituted aryl; -(Ci-Cealkylene)-aryl, wherein the alkylene and/or the alkyl group may be substituted; and phthalimidoCi-Csalkylene, wherein the phthalimido and/or the alkylene group may be substituted.

O

II

C 0 OM

Preferred mono organic peroxy acids and their salts are those of formula 19

wherein

M signifies hydrogen or an alkali metal, and

R'i9 signifies unsubstituted Ci-C 4 alkyl; phenyl;-Ci-C 2 alkylene-phenyl or

phthalimidoCi-Csalkylene.

Especially preferred is CH3COOOH and its alkali salts.

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

Also suitable are diperoxyacids, for example, 1 ,12-diperoxydodecanedioic acid (DPDA), 1 ,9-diperoxyazelaic acid, diperoxybrassilic acid, diperoxysebasic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1 ,4-diotic acid and 4,4'-sulphonylbisperoxybenzoic acid. In some cases the use of an additional bleach activator may be of advantage.

The term bleach activator is frequently used as a synonym for peroxyacid bleach precursor. All the above mentioned peroxy compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor.

Such precursors are the corresponding carboxyacid or the corresponding carboxyanhy- dride or the corresponding carbonylchlorid, or amides, or esters, which can form the peroxy acids on perhydrolysis. Such reactions are commonly known. Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988; 864,798; 907,356; 1 ,003,310 and 1 ,519,351 ; German Patent 3,337,921 ; EP-A-0185522; EP-A-0174132; EP-A-0120591 ; and U.S. Pat. Nos. 1 ,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.

Suitable bleach activators include the bleach activators, that carry O- and/or N-acyl groups and/or unsubstituted or substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED); acylated glycolurils, especially tetraacetyl glycol urea (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU); sodium-4- benzoyloxy benzene sulphonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4- sulphonate; sodium-4-methyl-3-benzoloxy benzoate; trimethyl ammonium toluyloxy- benzene sulphonate;acylated triazine derivatives, especially 1 ,5-diacetyl-2,4- dioxohexahydro-1 ,3,5-triazine (DADHT); compounds of formula (6):

wherein R22 is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R21 is linear or branched (C7-Cis)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-dihydrofuran; and also acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine 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 perimine acids with peroxides also come into consideration as bleach activators. Another useful class of peroxyacid bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Pat. Nos. 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-sulphonphenyl carbonate chloride - (SPCC), N-octyl,N,N-dimehyl-N10 -carbophenoxy decyl ammonium chloride - (ODC), 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate and Ν,Ν,Ν-trimethyl ammonium toluyloxy benzene sulphonate.

A further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520, WO 96/40661 and in European Patent Specification No.'s 458,396, 790244 and 464,880. These cationic nitriles also known as nitril quats have the formula (β)

wherein

R30 is a Ci-C24alkyl; a Ci-C24alkenyl; an alkaryl having a Ci-C24alkyl; a substituted d- C24alkyl; a substituted Ci-C24alkenyl; a substituted aryl,

R31 and R32 are each independently a Ci-C3alkyl; hydroxyalkyi having 1 to 3 carbon atoms,

-(C 2 H 4 0) n H, n being 1 to 6; -CH 2 -CN

R33 is is a Ci-C2oalkyl; a Ci-C2oalkenyl; a substituted Ci-C2oalkyl; a substituted

Ci-C2oalkenyl; an alkaryl having a Ci-C24alkyl and at least one other substituent, R34, R35, R36, R37 and R38 are each independently hydrogen, a Ci-Cioalkyl, a Ci-Cioalkenyl, a substituted Ci-Cioalkyl, a substituted Ci-Cioalkenyl, carboxyl, sulfonyl or cyano R38, R39, R40 and R41 are each independently a Ci-C6alkyl,

n' is an integer from 1 to 3,

n" is an integer from 1 to 16, and

X is an anion.

Other nitril quats have the following formula

R x-

42 R 45

R 4773 N ! C J— C≡N (ε)

R 44 R 46 wherein

R42 and R43 form, together with the nitrogen atom to which they are bonded, a ring comprising 4 to 6 carbon atoms, this ring may also be substituted by d-Cs-alkyl,

Ci-C5-alkoxy, d-Cs-alkanoyl, phenyl, amino, ammonium, cyano, cyanamino or chlo- ro and 1 or 2 carbon atom(s) of this ring may also be substituted by a nitrogen atom, by a oxygen atom, by a N-R47-group and/or by a R44-N-R47-group, wherein R47 is hy- drogen, d-Cs-alkyl, d-d-alkenyl, d-d-alkinyl, phenyl, d-Cg-aralkyl,

d-d-cycloalkyl, d-d-alkanoyl, cyanomethyl or cyano,

R44 is C1-C24-, preferably d-d-alkyl; d-d4- alkenyl, preferably d-d-alkenyl, cyanomethyl or d-d-alkoxy-d-d-alkyl,

R45 and R46 are independently from each other hydrogen; d-d-alkyl; d-d-alkenyl;

d-d-alkoxy-d-d-alkyl; phenyl or d-d-alkylphenyl, preferably hydrogen, methyl or phenyl, whereby preferably the moiety R45 signifies hydrogen, if R46 is not hydrogen, and

X- is an anion. uitable examples of nitril quats of formula (ε) are

and

Other nitrile quats have the formula

wherein

A is a saturated ring formed by a plurality of atoms in addition to the Ni atom, the saturated ring atoms to include at least one carbon atom and at least one heteroatom in addition to the Ni atom, the said one heteroatom selected from the group consisting of O, S and N atoms, the substituent R47 bound to the Ni atom of the Formula (φ) structure is (a) a C-i-Cs- alkyl or alkoxylated alkyl where the alkoxy is C2-4, (b) a C4-C24cycloalkyl, (c) a C 7 -C24alkaryl, (d) a repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is C2-4, or (e) -CR5oR5i-C≡N where R50 and R51 are each H, a Ci-C24alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C2-C4, in Formula (φ) at least one of the R½ and R49 substituents is H and the other of R48 and R49 is H, a Ci-C24alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C2-4, and Y is at least one counterion. 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 which is selected from the group consisting of tetraacetylethylenediamine, pentaacetylglucose, sodium oc- tanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium deca- noyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodeca- noyloxybenzenesulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, deca- noyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, oc- tanoyloxybenzene, nonanoyloxybenzene, decanoyloxybenzene, undecanoyloxybenzene and dodecanoyloxybenzene.

The activators may be used in an amount of up to 12 wt-%, preferably from 0.5-10 wt-% based on the total weight of the composition.

Since the compounds of the invention are used for the bleaching of stains or of soiling on textile materials or dishes in the context of a washing process or by the direct application of a stain remover, a further aspect of the invention is a detergent, cleaning or bleaching composition comprising

I) from 0 to 50 wt-%, based on the total weight of the composition, A) of at least one anionic surfactant and/or B) of a non-ionic surfactant,

II) from 0 to 70 wt-%, based on the total weight of the composition, C) of at least one builder substance,

III) from 1 - 99 wt-%, based on the total weight of the composition, D) of at least one peroxide and/or one peroxide-activator, O2 and/or air,

IV) E) at least one compound of formula (1 a) or (1 b) as described above in an amount that, in the liquor, gives a concentration of from 0.5 to 100 mg/litre of liquor, when from 0.5 to 50 g/litre of the detergent, cleaning, disinfecting or bleaching agent are added to the liquor,

V) from 0 - 20 wt-%, based on the total weight of the composition, of at least one further additive, and

VI) water ad 100 wt-%, based on the total weight of the composition.

The composition may optionally also contain water, or a filler material, such as Na2S0 4 . The sum of the components I) to IV) and optionally further components adds to 100%.

All wt-% are based on the total weight of the detergent, cleaning or bleaching composition.

The detergent, cleaning or bleaching compositions can be any kind of industrial or domestic cleaning or bleaching formulation.

The detergents may be in solid, liquid, gel-like or paste-like form. The detergents may also be in the form of powders or (super-)compact powders or granules, in the form of single- or multi-layer tablets (tabs), in the form of washing agent bars, washing agent blocks, washing agent sheets, washing agent pastes or washing agent gels, or in the form of powders, pastes, gels or liquids used in capsules or in pouches (sachets). When the composition is used in a washing process the concentration of the H2O2 or its precursor, such as perborate or percarbonate may vary in the range from 0.01 g/L to 15 g/L, preferably 0.03 g/L to 8 g/L and more preferably from 0.05 g/L to 2.5 g/L. If an additional activator is used, the activator, such as tetraacetylethylenediamine may vary 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 ) may vary from 1 μιτιοΙ/L to 1 mmol/L, preferably from 3 μιτιοΙ/L to 0.5 mmol/L, more preferably from 5 μιηοΙ/L to 0.3 mmol/L.

It is also possible to use additional bleach catalysts, which are commonly known, for exam- pie transition metal complexes as disclosed in EP 1 194514, EP 1383857 or WO04/007657.

When the detergent compositions according to the invention comprise a component A) and/or B), the amount thereof is preferably from 0.5 to 50 wt-%, especially from 0.5 to 30 wt-%.

When the detergent compositions according to the invention comprise a component C), the amount thereof is preferably from 1 to 70 wt-%, especially from 1 to 50 wt-%. Special preference is given to an amount of from 5 to 50 wt-% and especially an amount of from 10 to 50 wt-%.

The detergent composition according to the invention can be, for example, a peroxide- containing heavy-duty detergent or a separate bleaching additive, or a stain remover that is to be applied directly. A bleaching additive is used for removing coloured stains on textiles in a separate liquor before the clothes are washed with a detergent. A bleaching additive can also be used in a liquor together with a detergent.

Stain removers can be applied directly to the textile in question and are used especially for pretreatment in the event of heavy local soiling. The stain remover can be applied in liquid form, by a spraying method or in the form of a solid substance, such as a powder especially as a granule.

The 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 sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to an a-sulfonic fatty acid salt or an ester thereof.

Preferred sulfonates are, for example, alkylbenzenesulfonates having from 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radi- cal, alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical, and fatty acid salts derived from palm oil or tallow and having from 8 to 18 carbon atoms in the alkyl moiety. The average molar number of ethylene oxide units added to the alkyl ether sulfates is from 1 to 20, preferably from 1 to 10. The cation in the anionic surfactants is preferably an alkaline metal cation, especially sodium or potassium, more especially sodium. Pre- ferred carboxylates are alkali metal sarcosinates of formula Ri9-CON(R2o)CH2COOMi wherein R19 is Cg-C-izalkyl or Cg-C-izalkenyl, R20 is Ci-C4alkyl and Mi is an alkali metal, especially sodium. The non-ionic surfactant B) may be, for example, a primary or secondary alcohol ethox- ylate, especially a C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 mol of ethylene oxide per alcohol group. Preference is given to primary and secondary C10-C15 aliphatic alcohols ethoxylated with an average of from 1 to 10 mol of ethylene oxide per alcohol group. Non-ethoxylated non-ionic surfactants, for example alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamide), may likewise be used.

The total amount of anionic and non-ionic surfactants is preferably from 3 to 50 wt-%, especially from 5 to 40 wt-% and more especially from 5 to 30 wt-%. The lower limit of those surfactants to which even greater preference is given is 5 wt-%.

As builder substance C) there come into consideration, for example, alkali metal phosphates, especially tripolyphosphates, carbonates and hydrogen carbonates, especially their sodium salts, silicates, aluminum silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) and mixtures of such com- pounds.

Silicates that are especially suitable are sodium salts of crystalline layered silicates of the formula NaHSit02t+i.pH20 or Na2Sit02t+i .pH20 wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.

Among the 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.

Among the polycarboxylates, preference is given to polyhydroxycarboxylates, especially citrates, and acrylates, and also to copolymers thereof with maleic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylene- diamine disuccinate either in racemic form or in the enantiomerically pure (S,S) form.

Biodegradable options are, for example, aminoacid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Baypure CX (Lanx- ess).

Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1 , 1-diphosphonic acid, nitrilot- ris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethy- lenetriaminepentamethylenephosphonic acid, and also salts thereof. Also preferred poly- phosphonates have the following formula R lT N- (CH 2 CH 2 N) d -R 18

I

R 18

wherein

Ri8 is CH2PO3H2 or a water soluble salt thereof and

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

Especially preferred are the polyphosphonates wherein d is an integer of the value of 1

The compositions may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the classes bis-triazinylamino- stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis- benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative or couma- rin derivative or a pyrazoline derivative.

The compositions may furthermore comprise one or more further additives. Such additives are, 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 the spray drying and the granulating properties, for example sodium sulfate; perfumes; and also, if appropriate, antistatics and softening agents such as, for example, smectite; bleaching agents; pigments; and/or toning agents. These constituents should especially be stable to any bleaching agent employed.

If the detergent composition is used in an automatic dishwasher it is also common to use silver-corrosion inhibitors.

Such auxiliaries are added in a total amount of from 0.1 - 20 wt-%, preferably from 0.5 - 10 wt-%, especially from 0.5 - 5 wt-%, based on the total weight of the detergent formulation.

Furthermore, the detergent may optionally also comprise enzymes. Enzymes can be added for the purpose of stain removal. The enzymes usually improve the action on stains caused by protein or starch, such as, for example, blood, milk, grass or fruit juices. Preferred en- zymes are cellulases and proteases, especially proteases. Cellulases are enzymes that react with cellulose and its derivatives and hydrolyse them to form glucose, cellobiose and cellooligosaccharides. Cellulases remove dirt and, in addition, have the effect of enhancing the soft handle of the fabric. Lipases may also be present.

Examples of customary enzymes include, but are by no means limited to, the following: proteases as described in US-B-6 242 405, column 14, lines 21 to 32;

lipases as described in US-B-6 242 405, column 14, lines 33 to 46;

amylases as described in US-B-6 242 405, column 14, lines 47 to 56; and

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

Commercially available detergent proteases, such as Alcalase ® , Esperase ® , Everlase ® , Savinase ® , Kannase ® and Durazym ® , are sold e.g. by NOVOZYMES A S.

Commercially available detergent amylases, such as Termamyl ® , Duramyl ® , Stainzyme ® ,

Natalase ® , Ban ® and Fungamyl ® , are sold e.g. by NOVOZYMES A S. Commercially available detergent cellulases, such as Celluzyme ® , Carezyme ® and Endo- lase ® , are sold e.g. by NOVOZYMES A/S.

Commercially available detergent lipases, such as Lipolase ® , Lipolase Ultra ® and Lipo- prime ® , are sold e.g. by NOVOZYMES A/S.

Suitable mannanases, such as Mannanaway ® , are sold by NOVOZYMES A/S.

Beside in laundry care products, in a dishwashing detergents, 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 ® . The enzymes which may be used can, as described e.g. in International Patent Applications WO 92/1 1347 and WO 94/23005, be adsorbed on carriers and/or embedded in encapsulating substances in order to safeguard them against premature inactivation. They are present in the cleaning formulations according to the invention preferably in amounts not exceeding 5 wt-%, especially in amounts of from 0.1 wt-% to 1 .2 wt-%.

Amylases: The present invention preferably makes use of amylases having improved stability in detergents, especially improved oxidative stability. Such amylases are non-limitingly illustrated by the following: (a) An amylase according to WO 94/02597, Novo Nordisk A/S, published Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine (preferably threonine), of the methionine residue located in position 197 of the B.licheniformis alpha-amylase, known as TERMAMYL ® , or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B.subtilis, or B.stearothermophilus; (b) Stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha- amylases but that improved oxidative stability amylases have been made by Genencor from B. licheniformis NCIB8061 . Any other oxidative stability-enhanced amylase can be used.

Proteases: Protease enzymes are usually present in preferred embodiments of the invention at levels between 0.001 wt-% and 5 wt-%. The proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Suitable commercial proteolytic enzymes include Alcalase ® , Esperase ® , Durazyme ® , Savinase ® , Maxatase ® , Maxacal ® , and Maxapem ® 15 (protein engineered Maxacal). Purafect ® and subtilisin BPN and BPN' are also commercial- ly available.

When present, lipases comprise from about 0.001 wt-% to about 0.01 wt-% of the instant compositions and are optionally combined with from about 1 wt-% to about 5 wt-% of a surfactant having limesoap-dispersing properties, such as an alkyldimethylamine N-oxide or a sulfobetaine. Suitable lipases for use herein include those of bacterial, animal and fungal origin, including those from chemically or genetically modified mutants.

When incorporating lipases into the instant compositions, their stability and effectiveness may in certain instances be enhanced by combining them with small amounts (e.g., less than 0.5 wt-% of the composition) of oily but non-hydrolyzing materials.

The enzymes, when used, may be present in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5 wt-% and more especially from 0.1 to 4 wt-%, based on the total weight of the detergent formulation.

If the detergent formulation is a dishwashing detergent formulation, more preferably an automatic dishwashing detergent formulation, then it can optionally also comprise from about 0.001 wt-% to about 10 wt-%, preferably from about 0.005 wt-% to about 8 wt-%, most preferably from about 0.01 wt-% to about 6 wt-% of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, 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.

In order to enhance the bleaching action, the compositions may, in addition to comprising the catalysts described herein, also comprise photocatalysts the action of which is based on the generation of singlet oxygen.

Further preferred additives to the compositions according to the invention are dye-fixing agents and/or polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions. Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or pol- yvinylpyridine-N-oxides, which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range of from 5000 to 60 000, more especially from 10 000 to 50 000. Such polymers are usually used in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5 wt-%, more especially from 0.1 to 2 wt-%, based on the total weight of the detergent formulation. 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.

When the inventive detergent composition is used as hardsurface cleaner, especially when the composition is used in automatic dishwasher formulations then, it has been found out, that it is preferable to avoid the use of simple calcium-precipitating soaps as antifoams in the present compositions as they tend to deposit on the dishware. Indeed, phosphate esters are not entirely free of such problems and the formulator will generally choose to minimize the content of potentially depositing antifoams in the instant compositions. Other examples for foam suppressors are paraffin, paraffin/alcohol combinations, or bisfatty acid amides.

The dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations herein may also optionally contain one or more heavy metal chelating agents, such as hydroxyethyldiphosphonate (HEDP). More generally, chelating agents suitable for use herein can be selected from the group consisting of amino carboxylates, amino phos- phonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Other suitable chelating agents for use herein are the commercial DEQUEST series, and che- lants from Nalco, Inc.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetrace- tates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.

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 ethylenediaminetetrakis (methylenephosphonates).

Further biodegradable sequestrants are, for example, aminoacid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Bay pure CX. Preferably, the aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

A highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS").

If utilized, these chelating agents or transition-metal selective sequestrants will generally comprise from about 0.001 wt-% to about 10 wt-%, more preferably from about 0.05 wt-% to about 1 wt-% of the dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations herein.

Preferred dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations herein may additionally contain a dispersant polymer. When present, a dispersant polymer is typically at levels in the range from 0 wt-% to about 25 wt-%, preferably from about 0.5 wt-% to about 20 wt-%, more preferably from about 1 wt-% to about 8 wt-% of the detergent composition. Dispersant polymers are useful for improved filming performance of the present dishwasher detergent compositions, especially in higher pH embodiments, such as those in which wash pH exceeds about 9.5. Particularly preferred are polymers, which inhibit the deposition of calcium carbonate or magnesium silicate on dishware. Suitable polymers are preferably at least partially neutralized or alkali metal, ammonium or substituted ammonium (e.g., mono-, di- or triethanolammonium) salts of polycarboxylic acids. The alkali metal, especially sodium salts are most preferred. While the molecular weight of the polymer can vary over a wide range, it preferably is from about 1 ,000 to about 500,000, more preferably is from about 1 ,000 to about 250,000.

Unsaturated monomeric acids that can be polymerized to form suitable dispersant polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments containing no carboxylate radicals such as methyl vinyl ether, sty- rene, ethylene, etc. is suitable provided that such segments do not constitute more than about 50 wt-% of the dispersant polymer.

Copolymers of acrylamide and acrylate having a molecular weight of from 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 wt-%, preferably less than about 20 wt-% of the dispersant polymer can also be used. Most preferably, such dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0 wt-% to about 15 wt-%, based on the total weight of the polymer.

Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. Such copolymers contain as monomer units: a) from about 90 wt-% to about 10 wt-%, preferably from about 80 wt-% to about 20 wt-% acrylic acid or its salts and b) from about 10 wt-% to about 90 wt-%, preferably from about 20 wt-% to about 80 wt-% of a substituted acrylic monomer or its salt and have the general formula:

-[(C(R a )C(Rb)(C(0)ORc)] wherein the apparently unfilled valencies are in fact occupied by hydrogen and at least one of the substituents R a , Rb, or R c , preferably R a or Rb, is a 1 to 4 carbon alkyl or hydroxyalkyl group; R a or R b can be a hydrogen and R c can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein R a is methyl, Rb is hydrogen, and R c is sodium.

A suitable low molecular weight polyacrylate dispersant polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from about 1 ,000 to about 5,000. The most preferred polyacrylate copolymer for use herein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer comprising about 70 wt-% acrylic acid and about 30 wt-% methacrylic acid.

Other dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000. Yet other dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of this group. Other suitable dispersant polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates.

Yet another group of acceptable dispersants are the organic dispersant polymers, such as polyaspartate.

Depending on whether a greater or lesser degree of compactness is required, filler materials can also be present in the instant 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 wt-%, preferably from 0.1 wt-% to about 40 wt-% of the dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations. Preferred filler is sodium sulfate, especially in good grades having at most low levels of trace impurities.

Sodium sulfate used herein preferably has a purity sufficient to ensure it is non-reactive with bleach; it may also be treated with low levels of sequestrants, such as phosphonates or EDDS in magnesium-salt form. Note that preferences, in terms of purity sufficient to avoid decomposing bleach, applies also to pH-adjusting component ingredients, specifically including any silicates used herein. Organic solvents that can be used in the cleaning formulations according to the invention, especially when the latter are in liquid or paste form, include alcohols having from 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols having from 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and mixtures thereof, and the ethers derivable from the mentioned classes of compound. Such water-miscible solvents are present in the cleaning formulations according to the invention preferably in amounts not exceeding 20 wt-%, especially in amounts of from 1 wt-% to 15 wt-%.

Many dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations herein will be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions herein may have exceptionally low buffering capacity, or may be substantially unbuffered. Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled in the art.

Certain dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations, comprise a pH-adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders. The pH-adjusting 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 of above about 8, preferably from about 9.5 to about 1 1 . The preferred nonphosphate pH-adjusting component can be selected from the group consisting of:

(i) sodium carbonate or sesquicarbonate; (ii) sodium silicate, preferably hydrous sodium silicate having Si02:Na20 ratio of from about 1 :1 to about 2: 1 , and mixtures thereof with limited quantities of sodium metasilicate;

(iii) sodium citrate;

(iv) citric acid;

(v) sodium bicarbonate;

(vi) sodium borate, preferably borax;

(vii) sodium hydroxide; and

(viii) mixtures of (i)-(vii). Preferred embodiments contain low levels of silicate (i.e. from about 3 wt-% to about 10 wt- % Si0 2 ).

Illustrative of highly preferred pH-adjusting component systems of this specialized type are binary mixtures of granular sodium citrate with anhydrous sodium carbonate, and three- component mixtures of granular sodium citrate trihydrate, citric acid monohydrate and an- hydrous sodium carbonate.

The amount of the pH adjusting component in compositions used for automatic dishwashing is preferably from about 1 wt-% to about 50 wt-% of the composition. In a preferred embodiment, the pH-adjusting component is present in the composition in an amount from about 5 wt-% to about 40 wt-%, preferably from about 10 wt-% to about 30 wt-%.

For compositions herein having a pH between about 9.5 and about 1 1 of the initial wash solution, particularly preferred automatic dishwashing detergent formulations embodiments comprise, by weight of the automatic dishwashing detergent formulations, from about 5 wt- % to about 40 wt-%, preferably from about 10 wt-% to about 30 wt-%, most preferably from about 15 wt-% to about 20 wt-%, of sodium citrate with from about 5 wt-% to about 30 wt- %, preferably from about 7 wt-% to 25 wt-%, most preferably from about 8 wt-% to about 20 wt-% sodium carbonate.

The essential pH-adjusting system can be complemented (i.e. for improved sequestration in hard water) by other optional detergency builder salts selected from nonphosphate de- tergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and poly- carboxylates. Preferred are the alkali metals, especially sodium, salts of such materials. Alternate water-soluble, non-phosphorus organic builders can be used for their sequestering properties. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid; nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, ox- ydisuccinic acid, carboxymethoxysuccinic acid, mellitic acid, and sodium benzene polycarboxylate salts. Further biodegradable buildes are, for example, aminoacid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Baypure CX.

The detergent formulations can take a variety of physical forms such as, for example, powder granules, tablets (tabs), gel and liquid. Examples thereof include, inter alia, conventional high-performance detergent powders, supercompact high-performance detergent pow- ders and tabs. One important physical form is the so-called concentrated granular form, which is added to a washing machine.

Also of importance are so-called compact or supercompact detergents. In the field of deter- gent manufacture, there is a trend towards the production of such detergents that contain an increased amount of active substances. In order to minimize energy consumption during the washing procedure, compact or supercompact detergents need to act effectively at low washing temperatures, for example below 40°C, or even at room temperature (25°C). Such detergents usually contain only small amounts of fillers or of substances, such as sodium sulfate or sodium chloride, required for detergent manufacture. The total amount of such substances is usually from 0 to 10 wt-%, especially from 0 to 5 wt-%, more especially from 0 to 1 wt-%, based on the total weight of the detergent formulation. Such (super)compact detergents usually have a bulk density of from 650 to 1000 g/l, especially from 700 to 1000 g/l and more especially from 750 to 1000 g/l.

The detergent formulations can also be in the form of tablets (tabs). The advantages of tabs reside in the ease of dispensing and convenience in handling. Tabs are the most compact form of solid detergent formulation and usually have a volumetric density of, for example, from 0.9 to 1.3 kg/litre. To achieve rapid dissolution, such tabs generally contain special dissolution aids:

- carbonate/hydrogen carbonate/citric acid as effervescents;

- disintegrators, such as cellulose, carboxymethyl cellulose or cross-linked poly(N-vinyl- pyrrolidone);

- rapidly dissolving materials, such as sodium (potassium) acetates, or sodium (potassi- urn) citrates;

- rapidly dissolving, water-soluble, rigid coating agents, such as dicarboxylic acids.

The tabs may also comprise combinations of such dissolution aids.

The detergent formulation may also be in the form of an aqueous liquid containing from 5 wt-% to 50 wt-%, preferably from 10 wt-% to 35 wt-%, of water or in the form of a nonaqueous liquid containing no more than 5 wt-%, preferably from 0 wt-% to 1 wt-% of water. Non-aqueous liquid detergent formulations may comprise other solvents as carriers. Low molecular weight primary or secondary alcohols, for example methanol, ethanol, propanol and isopropanol, are suitable for that purpose. The solubilising surfactant used is preferably a monohydroxy alcohol but polyols, such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerol and 1 ,2- propanediol) can also be used. Such carriers are usually used in a total amount of from 5 wt-% to 90 wt-%, preferably from 10 wt-% to 50 wt-%, based on the total weight of the detergent formulation. The detergent formulations can also used in so-called "unit liquid dose" form.

Also an aspect of the invention is a granule comprising

a) from 1 - 99 wt-%, 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 - 99 wt-%, based on the total weight of the granule, of at least one binder, c) from 0 - 20 wt-%, based on the total weight of the granule, of at least one encapsulating material,

d) from 0 - 20 wt-%, based on the total weight of the granule, of at least one further additive and

e) from 0 - 20 wt-% based on the total weight of the granule, of water.

The granules according to the invention comprise a water-soluble organic polymer as binder. Such polymers may be used singly or in the form of mixtures of two or more polymers.

Water-soluble polymers that come into consideration are, for example, polyethylene glycols, copolymers of ethylene oxide with propylene oxide, gelatin, polyacrylates, polymeth- acrylates, polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, polyvinylimidazoles, poly- vinylpyridine-N-oxides, copolymers of vinylpyrrolidone with long-chain a-olefins, copoly- mers of vinylpyrrolidone with vinylimidazole, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinylpyrrolidone/dimethylaminopropyl acrylamides, quaternised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymers of vinylcaprolactam/ vinylpyrrolidone/dimethylaminoethyl methacrylates, copolymers of vinylpyrrolidone and methacrylamidopropyl-trimethylammonium chloride, terpolymers of caprolac- tam/vinylpyrrolidone/dimethylaminoethyl methacrylates, copolymers of styrene and acrylic acid, polycarboxylic acids, polyacrylamides, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate, copolymers of ethyl acrylate with methacrylate and methacrylic acid, copolymers of maleic acid with unsaturat- ed hydrocarbons, and also mixed polymerisation products of the mentioned polymers.

Of those organic polymers, special preference is given to polyethylene glycols, carboxymethyl cellulose, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also poly- acrylates, copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymathacrylates.

Encapsulating materials include especially water-soluble and water-dispersible polymers and waxes. Of those materials, preference is given to polyethylene glycols, polyamides, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymethacrylates. In a specific embodiment the granule is a coated granulate comprising

a) a core pellet comprising

5 to 40% by weight based on the weight of the total granule of an acylhydrazone of formula (1 a) or (1 b) and 1 % to 10% by weight based on the weight of the total granule of water and/or a water soluble polymer binder which is selected from the group consisting of polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, cellulose derivatives, carbohydrates, polyethyleneglycols and mixtures thereof; b) 0.1 % to 25% by weight based on the weight of the total granule of a subcoating comprising a polymer mixture of hydroxypropylmethylcellulose (HPMC) and methylcelluolose (MC) in a ratio by weight of from 2:1 to 8:1 ; c) optionally 1 % to 20% by weight based on the weight of the total granule of a topcoating comprising a fatty acid selected from nonadecanoic acid, stearic acid, palmitic acid, myristic acid and mixtures thereof; and d) other ingredients

the sum of components a) to d) adding to 100%.

In the context of this invention the terms granulate, granule and particulate composition are used as synonyms. The final two - layer coated granulate preferably has an average particle size (X50) of 400 μιτι to 1500 μιη.

The prepared core pellets are, if necessary, made round in a rounder (spheronizer) in order to remove any sharp, friable edges, and then dried (when aqueous methods are used).

The core granule particles are then coated with a first layer also called subcoating, preferably in a fluid bed or spouting bed coater. The polymer mixture of hydroxypropylmethylcellulose (HPMC) and methylcellulose (MC) preferably is dissolved in water and is then sprayed onto the granules.

Preferably the water based coating when applied contains at least 70% of HPMC and MC in a weight ratio of from 2: 1 to 8: 1 .

Specifically, the HPMC and MC grades are of low mol weight, and the HPMC is a mixture of HPMC 3 and HPMC 6, preferably a mixture of 1 :1 by weight.

HPMC and MC are nonionic cellulose ethers which are used in many different application fields. Chemically, part of the hydroxyl groups in the anhydroglucose units that build natural cellulose are substituted with methoxy groups in the case of MC, and both methoxy and hydroxy propoxy groups for the HPMC. A common way to designate the average level of substitution on the cellulose chain is to give the methoxyl content and the hydroxypropyl content in the product in wt-%. Both substitution levels and also the degree of polymerization have influence on the properties of the product. A commercial MC may have about 28 - 30 wt-% of methoxy group content, and a commercial HPMC may have about 28-30 wt-% of methoxy group content and 7-12 wt-% of hy- droxypropoxy group content. For coating purpose, low degree of polymerization is preferred in order to achieve low viscosity of the coating solution which is sprayed on the granules. Typically, the viscosity at 2,0 wt-%, in mPas is also displayed in the product description.

As an example, Tylose MOBS 3 P4 (Shin Etsu) is a product with methoxy group content of 28-30%, a hydroxypropoxy group content of 7-12%, and a viscosity within 2.4 - 3.6 mPas of a 2 wt-% solution in water at 20°C, measured with an Ubbelohde viscosimeter at 20°C."

When the subcoating process is complete, the molten fatty acid mixture is coated on the granules via melt coating technology, to give a second coating layer, also called topcoating. Optionally, a small amount of silica is added into the fluid bed after the melt coating is completed, to improve the flowability of the product.

Preferably the mixture contains more than 60% stearic acid. In a specific embodiment the mixture contains 75% stearic acid and 25% palmitic acid.

The final coated granules according to the invention may be white / off-white, or colored. In case of a colored granule, the dye may be located in the granule core and/or in any of the coating layers.

Further additives (d) that come into consideration are, for example, wetting agents, dust removers, water-insoluble or water-soluble dyes or pigments, and also dissolution accel- erators, optical brighteners and sequestering agents. Examples have already been given above.

Another aspect of the invention is a process for the bleaching of stains or of soiling on textile materials in the context of a washing process or by the direct application of a stain re- mover and for the cleaning of hard surfaces comprising

bringing into contact a textile material or a hard surface material in an aqueous medium, a compound of formula (1 a) or (1 b) as described above and a peroxide or a peroxide- precursor or O2 and/or air.

Yet another aspect of the invention is the use, as a catalyst for oxidation reactions, of at least one compound of formula (1 a) or (1 b)

wherein in formula (1 a)

Q is Ci-C4alkylene

R 1 , R 2 , R 3 and R 4 independently from each other are Ci-Cisalkyl or

Q, R 1 and R 3 together with the nitrogen atoms to which they are bonded form a 5, 6 or 7 membered heterocyclic ring system;

R5, R 6 , R 9 and R 10 are hydrogen or Ci-Ci 8 alkyl;

R 7 , R 8 , R 11 and R 12 are independently hydrogen, Ci-Cisalkyl, Ci-Cisalkoxy, halogen or N0 2 ;

k is an integer from 1 to 8, preferably from 1 to 4;

X- and Y- are the same or different and are the anions of an inorganic or organic acid; wherein in formula (1 b) R 1 and R 2 independently from each other are Ci-Cisalkyl or together with the nitrogen atom to which they are bonded form a heterocyclic 5, 6 or 7 membered ring system which may contain an additional N or O atom;

and the other definitions are the same as defined in formula (1 a).

Preferably the compounds of formula (1 a) or (1 b) are used as catalysts together with peroxide or a peroxide-precursor, O2 and/or air for the bleaching of stains or of soiling on textile materials in the context of a washing process or by the direct application of a stain remover; for the cleaning of hard surfaces.

In a specific embodiment an additional bleach activator is used together with the compound of formula (1 ) and a peroxide or a peroxide-precursor, O2 and/or air.

In another specific embodiment a metal chelating agent (sequestrant) is used together with the compound of formula (1 ) and a peroxide or a peroxide-precursor, O2 and/or air.

In many cases the bleach activator and the metal chelating agent (sequestrant) are used together with the compound of formula (1 ) and a peroxide or a peroxide-precursor, O2 and/or air.

Definitions and preferences given above apply equally for all aspects of the invention. The following examples illustrate the invention. A) Synthesis Examples

Compound 1

b) N-[(E)-(2^ydroxyphenyl)methyleneamino]-2-[4-[2-[(2E)-2-[(2-h ydroxyphen

yl)methylene] hydrazino]-2-oxo-ethyl]- 1 ,4-dimethyl-piperazine- 1,4-diium- 1-yl] acetamide dichloride: A mixture of 2-[4-(2-hydrazino-2-oxo-ethyl)-1 ,4-dimethyl-piperazine-1 ,4-diium-1- yl]aceto hydrazide dichloride (prepared as described below; 3.2g, 9.66mmol), salicylate- hyde (2.95g, 24.2mmol) and ethanol (20ml) was stirred at 60°C until the starting material disappeared (48 hours), the reaction being followed by TLC. The reaction mixture was cooled to 10°C and filtered. The wet filter cake (7.5g) was taken into water (80ml), heated to reflux and the resulting dispersion cooled to 25°C. Ethanol (30ml) was added, the result- ing suspension filtered and the filter cake dried in a vacuum oven at 50°C to afford the title compound (3.48g) as white solid, mp. 228 - 233°C (dec);

MS (pos. ESI), m/z (%): found 234 (100; [M ++ -2CI]); calcd. for C24H32N6O4, z = 2: 234; elemental analysis (%): found CI, 12.6; calcd. for C24H32N6O4 2CI: CI, 13.1 ;

1 H-NMR (400MHz, DMSO-d 6 ), S[ppm]\ 3.58 (s) and 3.62 (s; 6H), 4.14 - 4.37 (m, 8H), 4.84 (s) and 5.20 - 5.22 (m, d-like; 4H), 6.87 - 6.99 (m), 7.26 - 7.34 (m), 7.61 - 7.63 (m) and 7.79 - 7.80 (m; 8H), 8.43 (br s) and 8.63 (br s; 2H), 10.23 (s), 10.24 (s), 10.80 (s) and 10.82 (s; 2H), 12.09 (br s) and 13.15 (br s; 2H). a) 2-[4-(2-Hydrazino-2-oxo-ethyl)- 1 ,4-dimethyl-piperazine- 1,4-diium- 1-yl]aceto hydrazide dichloride: A mixture of ethyl 2-[4-(2-ethoxy-2-oxo-ethyl)-1 ,4-dimethyl-piperazine-1 ,4-diium- 1-yl]acetate dichloride (5g, 13.9mmol; prepared from ethyl chloroacetate and Ν,Ν'- dimethylpiperazine according to Z. Dega-Szafran et al., Journal of Molecular Structure 2002, 614, 23-32), hydrazine monohydrate (3.77g, 75.3mmol) and ethanol (30ml) was stirred at 35°C until the starting material disappeared (36 hours), the reaction being followed by 1 H-NMR. The reaction mixture was cooled to 25°C, filtered and the filter cake dried in a vacuum oven at 60° to afford the title compound (3.95g) as a white solid, mp. 202 - 204°C (dec);

MS (pos. ESI), m/z (%): found 130 (10; [M ++ -2CI]); calcd. for C 1Q H 24 N 6 0 2 , z = 2: 130; elemental analysis (%): found CI, 21.0; calcd. for CioH 2 4N 6 C>2 » 2CI: CI, 21 .4;

1 H-NMR (400MHz, D 2 0), J[ppm]: 3.46 (s, 6H), 4.10 - 4.13 (m, d-like, 4H), 4.34 (s, 4H), 4.34 - 4.37 (m, d-like, 4H). Compound 2

b) [2-[(2E)-2-[(2^ydroxyphenyl)methylene]hydrazino]-2-oxo-ethyl ]-[2-[[2-[(2^^

hydroxyphenyl)methylene]hydrazino]-2-oxo-ethyl]-dimethyl- am

ammonium dibromide: A mixture of (2-hydrazino-2-oxo-ethyl)-[2-[(2-hydrazino-2-oxo-ethyl)- dimethyl-ammonio]ethyl]-dimethyl-ammonium di bromide (prepared as described below; 4g, 9.47mmol), salicylaldehyde (3.05g, 25mmol) and ethanol (20ml) was stirred until the starting material disappeared, initially at 50°C (12 hours), then at 60°C (48 hours), then left without stirring at 25°C (1 week) and again stirred at 60°C (12 hours), the reaction being followed by 1 H-NMR. The reaction mixture was cooled to 25°C and filtered, the wet filter cake (7.4g) taken into water (80ml), heated to reflux and the resulting solution cooled to 0°C. The resulting suspension was filtered and the filter cake dried in a vacuum oven at 40°C to afford the title compound (3.8g) as white solid, mp. 226 - 227°C (dec);

MS (pos. ESI), m/z (%): found 235 (100; [M ++ -2Br]); calcd. for C24H34N6O4, z = 2: 235; elemental analysis (%): found Br, 25.4; calcd. for C 2 4H 3 4N 6 04-2Br: Br, 25.35;

1 H-NMR (400MHz, DMSO-d 6 ), [ppm]: 3.40 (s), 3.41 (s) and 3.44 (s; 12H), 4.33 (s) and 4.35 (s; 4H), 4.42 (s), 4.43 (s), 4.87 (s) and 4.88 (s; 4H), 6.87 - 6.95 (m), 7.25 - 7.34 (m), 7.59 - 7.64 (m) and 7.79 - 7.83 (m; 8H), 8.41 (s), 8.55 (s) and 8.56 (s; 2H), 10.08 (s), 10.09 (s), 10.72 (s) and 10.73 (s; 2H), 1 1 .97 (br s) and 12.38 (br s; 2H). a) (2-Hydrazino-2-oxo-ethyl)-[2-[(2-hydrazino-2-oxo-ethyl)-dime thyl-ammonio] ethyl]- dimethyl-ammonium dibromide: A mixture of (2-ethoxy-2-oxo-ethyl)-[2-[(2-ethoxy-2-oxo- ethyl)-dimethyl-ammonio]ethyl]-dimethyl-ammonium dibrom ide (5g, 1 1.1 mmol; prepared according to N. Sugimoto et al., Tetrahedron 2008, 64, 168-174), hydrazine monohydrate (1.94g, 38.9mmol) and ethanol (30ml) was stirred at 25°C until the starting material disappeared (12 hours), the reaction being followed by 1 H-NMR. The reaction mixture was filtered and the filter cake dried to afford the title compound (3.9g) as a white solid, mp. 188 - 189°C (dec); MS (pos. ESI), m/z (%): found 131 (25; [M ++ -2Br]); calcd. for CioH 2 6N 6 02, z 1 H-NMR (400MHz, D 2 0), S[ppm]\ 3.35 (s, 12H), 4.14 (s, 4H), 4.27 (s, 4H). Compound 3

b) N-[(E)-(2-Hydroxyphenyl)methyleneamino]-2-[4-[2-[(2E)-2-[(2- hydroxyphen

yl)methylene]hydrazino]-2-oxo-ethyl]morpholin-4-ium-4-yl] acetamide bromide:

A mixture of 2-[4-(2-hydrazino-2-oxo-ethyl)morpholin-4-ium-4-yl]acetohydr az ide bromide (prepared as described below; 5g, 16mmol), salicylaldehyde (5.93g, 48.6mmol) and methanol (5ml) was stirred until the starting material disappeared, initially at 25°C (1 hour), then at 80°C (24 hours), the reaction being followed by 1 H-NMR. The reaction mixture was cooled to 25°C, filtered and the filtrate concentrated on a rotary evaporator, yielding an orange oil (9.6g). Column chromatography (silica gel, ethylacetate / methanol as eluent) afforded the title compound as an off-white solid (4.7g), mp. >120°C (dec);

MS (pos. ESI), m/z (%): found 440 (100; [M + -Br]); calcd. for C22H26N5O5: 440; 1 H-NMR (400MHz, DMSO-d 6 ), [ppm]: 1.18 (t, residual ethylacetate; 3.8%), 1 .99 (s, ethylacetate), 4.03 (q, ethylacetate), 4.03 (br s) and 4.09 (br s; 8H), 4.76 (s), 4.83 (s), 5.19 (s), 5.24 (s; 4H), 6.86 - 6.93 (m), 7.25 - 7.33 (m), 7.57 - 7.60 (m) and 7.80 - 7.82 (m; 8H), 8.38 (s), 8.39 (s), 8.49 (s) and 8.50 (s; 2H), 10.08 (br s), 10.71 (br s) and 10.78 (br s; 2H), 1 1.95 (br s) and 12.37 (br s; 2H). a) 2-[4-(2-Hydrazino-2-oxo-ethyl)morpholin-4-ium-4-yl]acetohydr azide brom ide: tK mixture of ethyl 2-[4-(2-ethoxy-2-oxo-ethyl)morpholin-4-ium-4-yl]acetate bromide (1g, 2.9mmol; prepared according to R. C. Duty et al., J. Org. Chem. 1970, 35(6), 1800 - 1802), hydrazine monohydrate (0.59g, 1 1.8mmol) and methanol (15ml) was stirred at 25°C until the starting material disappeared (12 hours), the reaction being followed by 1 H-NMR. The emulsion was allowed to settle and the lower oily phase separated off. Upon washing with methanol, the lower oily phase solidified, affording the title compound as white solid (0.75g), mp. >72°C (dec);

LC-MS (pos. ESI), m/z (%): found 232 (100; [M + -Br]); calcd. for C 8 Hi8N 5 0 3 : 232. B) Application Examples

Compound 1

Comparative

Example 1 - Application: (Peroxide Bleaching in Presence of TAED)

50 g of white cotton fabric and 0.5g each BC01 (tea stain), BC02 (coffee stain), BC03 (tea stain), CS12 (red currant stain) on cotton fabric are treated in 250 ml of washing liquor. The liquor contains AATCC standard detergent in a concentration of 4.5 g/l, and 0.65g/l sodium percarbonate (SPC), 144mg TAED, tap water. The sequestrant 1 -Hydroxy-ethylenidine-1 ,1- diposphonic acid (HEDP) is added to an amount of 1 % on weight of detergent. The catalysts were added in the concentrations given in table 1. "Comparative" was dissolved in ethanol, Compound 1 was added as a suspension in ethanol.

The washing process is carried out in a steel beaker in a LINITEST apparatus for 60 minutes at 40°C. For evaluating the bleaching results, the increase in the lightness ΔΥ (difference in lightness according to CIE) of the stains brought about by the treatment is determined spectrophotometrically . The higher the ΔΥ value, the better the bleach perfor- mance

Table 1 Bleach Results with SPC/TAED at 40°C

Comparative BC01 BC02 BC03 CS12

3.1 ppm 15 1 1.1 19.2 51.8

6.3 ppm 16.4 1 1.8 20.5 53

9.4 ppm 16.9 12.3 22.5 52.9

12.5 ppm 15.4 1 1.3 19.7 50

Compound 1 BC01 BC02 BC03 CS12

2.7 ppm 14.9 1 1.1 19 52.1

5.4 ppm 16.2 12.3 20 53.1

8.1 ppm 17.1 12.9 21 .9 53.4

10.8 ppm 18.6 13.8 22.1 53.7 The results show that application of Compound 1 at lower concentrations results in a better or at least similar bleach than "Comparative" .

Example 2 - Application: (Peroxide Bleaching)

50 g of white cotton fabric and 0.5g each BC01 (tea stain), BC02 (coffee stain), BC03 (tea stain), CS12 (red currant stain) on cotton fabric are treated in 250 ml of washing liquor. The liquor contains AATCC standard detergent in a concentration of 4.5 g/l, and 0.65g/l sodium percarbonate (SPC), tap water. The sequestrant 1 -Hydroxy-ethylenidine-1 ,1-diposphonic acid (HEDP) is added to an amount of 1 % on weight of detergent. The catalysts were add- ed in the concentrations given in table 1. "Comparative" was dissolved in ethanol, Compound 1 was added as a suspension in ethanol.

The washing process is carried out in a steel beaker in a LINITEST apparatus for 60 minutes at 40°C. For evaluating the bleaching results, the increase in the lightness ΔΥ (difference in lightness according to CIE) of the stains brought about by the treatment is determined spectrophotometrically . The higher the ΔΥ value, the better the bleach performance

Table 2 Bleach Results with SPC at 40°C

The results show that application of Compound 1 at lower concentrations results in better bleach than "Comparative".




 
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