WO2000060043A1 - Composition and method for bleaching a substrate - Google Patents
Composition and method for bleaching a substrate Download PDFInfo
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- WO2000060043A1 WO2000060043A1 PCT/EP2000/002587 EP0002587W WO0060043A1 WO 2000060043 A1 WO2000060043 A1 WO 2000060043A1 EP 0002587 W EP0002587 W EP 0002587W WO 0060043 A1 WO0060043 A1 WO 0060043A1
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- optionally substituted
- alkyl
- ligand
- bleaching
- methyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/55—Acids; Esters
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents
Definitions
- This invention relates to compositions and methods for catalytically bleaching substrates with atmospheric oxygen, more particularly using a defined class of ligand or complex as catalyst, and further relates to ligands and complexes useful in such compositions and methods.
- This invention also relates to a method of treating textiles, such as laundry fabrics, using the defined class of ligand or complex as catalyst, more specifically to a method whereby bleaching by atmospheric oxygen is catalysed after the treatment.
- Peroxygen bleaches are well known for their ability to remove stains from substrates.
- the substrate is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals, such as inorganic or organic peroxides.
- these systems must be activated.
- One method of activation is to employ wash temperatures of 60°C or higher. However, these high temperatures often lead to inefficient cleaning, and can also cause premature damage to the substrate.
- a preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. For example, various European systems are based on tetraacetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate, whereas in the United States laundry bleach products are typically based on sodium nonanoyloxybenzenesulfonate (SNOBS) as the organic precursor coupled with sodium perborate.
- TAED tetraacetyl ethylenediamine
- SNOBS sodium nonanoyloxybenzenesulfonate
- Precursor systems are generally effective but still exhibit several disadvantages. For example, organic precursors are moderately sophisticated molecules requiring multi-step manufacturing processes resulting in high capital costs. Also, precursor systems have large formulation space requirements so that a significant proportion of a laundry powder must be devoted to the bleach components, leaving less room for other active ingredients and complicating the development of concentrated powders. Moreover. precursor systems do not bleach very efficiently in countries where consumers have wash habits entailing low dosage, short wash times, cold temperatures and low wash liquor to substrate ratios.
- hydrogen peroxide and peroxy systems can be activated by bleach catalysts, such as by complexes of iron and the ligand N4Py (i.e. N. N- bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine) disclosed in WO95/34628. or the ligand Tpen (i.e. N, N, N ⁇ N'-tetra(pyridin-2-yl-methyl)ethylenediamine) disclosed in WO97/48787.
- molecular oxygen may be used as the oxidant as an alternative to peroxide generating systems.
- no role in catalysing bleaching by atmospheric oxygen in an aqueous medium is reported.
- WO 97/38074 reports the use of air for oxidising stains on fabrics by bubbling air through an aqueous solution containing an aldehyde and a radical initiator.
- a broad range of aliphatic, aromatic and heterocyclic aldehydes is reported to be useful, particularly para-substituted aldehydes such as 4-methyl-. 4-ethyl- and 4- isopropyl benzaldehyde, whereas the range of initiators disclosed includes N- hydroxysuccinimide, various peroxides and transition metal coordination complexes.
- the aldehyde component and radical initiators such as peroxides are consumed during the bleaching process.
- These components must therefore be included in the composition in relatively high amounts so as not to become depleted before completion of the bleaching process in the wash cycle.
- the spent components represent a waste of resources as they can no longer participate in the bleaching process.
- the present invention provides a bleaching composition
- a bleaching composition comprising, in an aqueous medium, atmospheric oxygen and a ligand which forms a complex with a transition metal, the complex catalysing bleaching of a substrate by the atmospheric oxygen, wherein the aqueous medium is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.
- the medium is therefore preferably insensitive or stable to catalase. which acts on peroxy species.
- the present invention provides a method of bleaching a substrate comprising applying to the substrate, in an aqueous medium, a ligand which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by- atmospheric oxygen.
- the present invention provides the use of a ligand which forms a complex with a transition metal as a catalytic bleaching agent for a substrate in an aqueous medium substantially devoid of peroxygen bleach or a peroxy-based or - generating bleach system, the complex catalysing bleaching of the substrate by the atmospheric oxygen.
- the present invention provides a method of treating a textile by contacting the textile with a ligand which forms a complex with a transition metal, whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment.
- the present invention provides a dry textile having a ligand as defined above applied or deposited thereon, whereby bleaching by atmospheric oxygen is catalysed on the textile.
- the present invention provides ligands and complexes, as defined further below.
- the method according to the present invention permits all or the majority of the bleaching species in the medium (on an equivalent weight basis) to be derived from atmospheric oxygen.
- the medium can be made wholly or substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.
- the complex is a catalyst for the bleaching process and. as such, is not consumed but can continue to participate in the bleaching process.
- the catalytically activated bleaching system of the type in accordance with the present invention which is based on atmospheric oxygen, is therefore both cost-effective and environmentally friendly.
- the bleaching system is operable under unfavourable wash conditions which include low temperatures, short contact times and low dosage requirements.
- the method is effective in an aqueous medium and is therefore particularly applicable to bleaching of laundry fabrics. Therefore, whilst the composition and method according to the present invention may be used for bleaching any suitable substrate, the preferred substrate is a laundry fabric.
- the bleaching method may be carried out by simply leaving the substrate in contact with the medium for a sufficient period of time. Preferably, however, the aqueous medium on or containing the substrate is agitated.
- An advantage of the method according to the fourth aspect of the invention is that, by enabling a bleaching effect even after the textile has been treated, the benefits of bleaching can be prolonged on the textile. Furthermore, since a bleaching effect is conferred to the textile after the treatment, the treatment itself, such as a laundry wash cycle, may for example be shortened. Moreover, since a bleaching effect is achieved by atmospheric oxygen after treatment of the textile, hydrogen peroxide or peroxy-based bleach systems can be omitted from the treatment substance.
- the ligand may be present as a preformed complex of a ligand and a transition metal.
- the composition may comprise a free ligand that complexes with a transition metal already present in the water or that complexes with a transition metal present in the substrate.
- the composition may also be formulated as a composition of a free ligand or a transition metal-substitutable metal-ligand complex, and a source of transition metal, whereby the complex is formed in situ in the medium.
- the ligand forms a complex with one or more transition metals, in the latter case for example as a dinuclear complex.
- Suitable transition metals include for example: manganese in oxidation states II-V, iron Il-V. copper I-III. cobalt I-III. titanium Il-IV. tungsten IV- VI, vanadium II-V and molybdenum II-VI.
- the ligand forms a complex of the general formula (Al):
- M represents a metal selected from Mn(II)-(III)-(IV)-(V). Cu(I)-(II)-(III), Fe(II)- (III)-(IV)-(V), Co(I)-(II)-(III), Ti(II)-(III)-(IV), V(II)-(III)-(IV)-(V). Mo(II)-(III)-(I V)-(V)- (VI) and W(IV)-(V)-(VI), preferably selected from Fe(II)-(III)-(IV)-(V);
- L represents a ligand as herein defined, or its protonated or deprotonated analogue
- X represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner, preferably selected from O 2" , RBO 2 2 ⁇ RCOO “ . RCONR “ . OH “ , NO 3 “ , NO. S 2 ⁇ RS “ , PO 4 3 ⁇ PO 3 OR 3” , H 2 O, CO 3 2 ⁇ HCO 3 " , ROH, N(R) 3 . ROO “ , O 2 2 ⁇ O 2 " . RCN, Cl “ , Br “ , OCN “ , SCN “ , CN “ , N 3 ⁇ F “ , I “ , RO “ , ClO 4 " .
- Y represents any non-coordinated counter ion, preferably selected from ClO 4 " , BR 4 " , [MX4] “ , [MX4] 2" , PF 6 “ , RCOO “ , NO 3 “ , RO “ , N + (R) 4 , ROO “ , O 2 2” , O 2 ⁇ Cl ' , Br “ , F ' , I “ , CF 3 SO 3 “ , S 2 O 6 2' , OCN “ , SCN “ , H 2 O, RBO 2 2” , BF 4 " and BPli-* ' , and more preferably selected from ClO 4 ⁇ BR 4 ' , [FeCl 4 ] “ , PF 6 “ , RCOO “ , NO 3 ' , RO “ , N + (R) 4 , Cl “ , Br “ , F “ , I “ , CF 3 SO 3 ⁇ S 2 O 6 2” , OCN
- R' represents cycloalkyl. aryl. arylalkyl. or alkyl optionally substituted by -F. -Cl, -Br, -I, -NH 3 ⁇ -SO 3 H, -SO 3 " (Na T , KT). -COOH. -COO " (Na + . K + ), -P(O)(OH) 2 , or -P(O)(O ' (Na ⁇ K + )) 2 . and preferably each R independently represents hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or optionally substituted phenyl. naphthyl or C ⁇ - -alkyl.
- the ligand L is of the general formula (I):
- Qi- Q 2 - Qi- Q 4 and Q independently represent a group of the formula:
- Y independently represents a group selected from -O-, -S-, -SO-, -SO 2 -, -C(O)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(O)- and -(G)N- , wherein G is selected from hydrogen, alkyl, aryl. arylalkyl. cycloalkyl. each except hydrogen being optionally substituted by one or more functional groups E;
- R5, R6, R7, R8 independently represent a group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6, or R7 together with R8, or both, represent oxygen, or R5 together with R7 and/or independently R6 together with R8, or R5 together with R8 and/or independently R6 together with R7, represent C ⁇ .
- R t . R 2 . R 3 . R4 comprise coordinating heteroatoms and no more than six heteroatoms are coordinated to the same transition metal atom.
- At least two. and preferably at least three, of Ri. R 2 . R 3 . independently represent a group selected from carboxylate. amido. -NH-C(NH)NH 2 . hydroxyphenyl. an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine. pyrazine, pyrazole, imidazole. benzimidazole. quinoline. quinoxaline. triazole. isoquinoline. carbazole. indole. isoindole. oxazole and thiazole.
- R 3 . R*. when representing a heterocyclic or heteroaromatic ring are selected from C -alkyl. aryl, arylalkyl. heteroaryl. methoxy, hydroxy. nitro. amino. carboxyl, halo, and carbonyl.
- the groups R5, R6. R7. R8 preferably independently represent a group selected from - H. hydroxy-Co-C 0 -alkyl. halo-C 0 -C 2 o-alkyl. nitroso. fo ⁇ myl-Co-C 2 o-alkyl. carboxyl-Co- C 20 -alkyl and esters and salts thereof. carbamoyl-Co-C 2 o-alkyl. sulfo-Co-C 2 o-alkyl and esters and salts thereof, sulfamoyl-C 0 -C 2 o-alkyl, amino-Co-Cio-alkyl.
- aryl-Co-C 2 o-alkyl Co-C 20 -alkyl, alkoxy-C 0 -C 8 -alkyl. carbonyl-C 0 -C 6 -alkoxy, and C 0 -C 20 -alkylamide.
- R6-R8 is linked together.
- the groups Qi, Q 2 , Q 3 , Q 4 preferably independently represent a group selected from CH 2 - and -CH 2 CH 2 -.
- Group Q is preferably a group selected from -(CH 2 ) 2 -4-, -CH 2 CH(OH)CH2-.
- R represents -H or C ⁇ - 4 -alkyl.
- the ligand L is of the general formula (II):
- Ri, R 2 , R 3 , R t . R7. R8 are independently defined as for formula (I).
- Preferred classes of ligands according to the first preferred embodiment, as represented by formula (II) above, are as follows:
- Ri, R 2 , R 3 , R- t each independently represent a coordinating group selected from carboxylate, amido, -NH-C(NH)NH 2 , hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline. triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.
- Ri, R 2 , R 3 , R each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl. optionally substituted imidazol-4-yl, optionally substituted pyrazol-1-yl, and optionally substituted quinolin-2-yl.
- Ri. R 2 . R 3 each independently represent a coordinating group selected from carboxylate. amido, -NH-C(NH)NH 2 . hydroxyphenyl. an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine. pyrimidine, pyrazine. pyrazole. imidazole. benzimidazole. quinoline. quinoxaline. triazole. isoquinoline. carbazole. indole. isoindole. oxazole and thiazole: and
- Rt represents a group selected from hydrogen.
- C 1 . 20 optionally substituted alkyl.
- C ⁇ - 0 optionally substituted arylalkyl.
- Ri, R 2 , R 3 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl. optionally substituted imidazol-2-yl. optionally substituted imidazol-4-yl. optionally substituted pyrazol-1-yl. and optionally substituted quinolin-2-yl; and
- R-4 represents a group selected from hydrogen. Cj.io optionally substituted alkyl, C ⁇ - 5 -furanyl, C 1 . 5 optionally substituted benzylalkyl. benzyl. C 1 . 5 optionally substituted alkoxy, and C ⁇ . 20 optionally substituted N + Me 3 .
- Ri, R 4 each independently represent a coordinating group selected from carboxylate, amido, -NH-C(NH)NH 2 , hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole. quinoline, quinoxaline. triazole, isoquinoline, carbazole, indole. isoindole. oxazole and thiazole; and
- R 2 , R3 each independently represent a group selected from hydrogen, C 1 - 20 optionally substituted alkyl, C1- 20 optionally substituted arylalkyl. aryl, and C
- . 20 optionally substituted NR 3 + (wherein R C ⁇ . 8 -alkyl).
- R 4 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl. optionally substituted imidazol-2-yl. optionally substituted imidazol-4-yl. optionally substituted pyrazol-l-yl. and optionally substituted quinolin-2-yl: and
- R . R 3 each independently represent a group selected from hydrogen. C ⁇ - ⁇ o optionally substituted alkyl. C ⁇ - 5 -furanyl, C 1 . 5 optionally substituted benzylalkyl. benz ⁇ l. C ⁇ - 5 optionally substituted alkoxy, and C ⁇ _ 2 o optionally substituted N ⁇ Me 3 .
- Y in formula (Al) balance the charge z on the complex formed by the ligand L. metal M and coordinating species X.
- Y may be an anion such as RCOO " . BPh-f. ClO-f. BF “ . PF 6 " . RSO 3 " , RSO 4 " . SO 2" . NO 3 " . F “ . Cl “ . Br “ . or I “ . with R being hydrogen, optionally substituted alkyl or optionally substituted aryl.
- Y may be a common cation such as an alkali metal, alkaline earth metal or (alkyl)ammonium cation.
- the ligand forms a complex of the general formula (I) as defined above, but wherein L represents a pentadentate or hexadentate ligand of general formula (III):
- each R 1 independently represents -R 3 -V, in which R 3 represents optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl;
- W represents an optionally substituted alkylene bridging group selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 -C 6 H 4 -CH 2 -, -CH 2 -C 6 H,o-CH 2 -, and -CH 2 -C ⁇ 0 H 6 -CH 2 -; and R 2 represents a group selected from R 1 . and alkyl. aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy. alkoxy. phenoxy. carboxylate, carboxamide. carboxylic ester, sulfonate. amine.
- R 4 is selected from hydrogen, alkanyl. alkenyl. arylalkanyl. arylalkenyl. oxyalkanyl, oxyalkenyl. aminoalkanyl. aminoalkenyl. alkanyl ether and alkenyl ether.
- the ligand L having the general formula (III), as defined above, is a pentadentate ligand
- R R
- pentadentate is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex.
- 'hexadentate' is meant that six hetero atoms can in principle coordinate to the metal M ion.
- one of the arms will not be bound in the complex, so that the hexadentate ligand will be penta coordinating.
- two hetero atoms are linked by the bridging group W and one coordinating hetero atom is contained in each of the three R 1 groups.
- the coordinating hetero atoms are nitrogen atoms.
- the ligand L of formula (III) comprises at least one optionally substituted heteroaryl group in each of the three R 1 groups.
- the heteroaryl group is a pyridin-2-yl group, in particular a methyl- or ethyl-substituted pyridin-2-yl group.
- the heteroaryl group is linked to an N atom in formula (III), preferably via an alkylene group, more preferably a methylene group.
- the heteroaryl group is a 3-methyl- pyridin-2-yl group linked to an N atom via methylene.
- the group R in formula (III) is a substituted or unsubstituted alkyl, aryl or arylalkyl group, or a group R 1 .
- R 2 is different from each of the groups R 1 in the formula above.
- R is methyl, ethyl, benzyl, 2-hydroxyethyl or 2- methoxyethyl. More preferably, R 2 is methyl or ethyl.
- the bridging group W may be a substituted or unsubstituted alkylene group selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 -C 6 H4-CH 2 -, -CH 2 -C 6 H, 0 - CH 2 -. and -CH 2 -C ⁇ 0 H 6 -CH 2 - (wherein -C ⁇ LLr. -C ⁇ Hio-. -C ⁇ 0 H 6 - can be ortho-. para-, or meta-C& -. -C H 10 -. -C ⁇ oH 6 -).
- the bridging group W is an ethylene or 1.4- butylene group, more preferably an ethylene group.
- V represents substituted pyridin-2-yl. especially methyl-substituted or ethyl- substituted pyridin-2-yl, and most preferably V represents 3 -methyl pyridin-2-yl.
- Suitable counter ions Y include those which give rise to the formation of storage-stable solids.
- Preferred counter ions for the preferred metal complexes are selected from R 7 COO " . ClO 4 " . BF 4 “ . PF 6 “ . RSO 3 “ (in particular CF 3 SO 3 “ ), RSO 4 “ . SO 4 2” . NO 5 " . F.
- the complex (Al) can be formed by any appropriate means, including in situ formation whereby precursors of the complex are transformed into the active complex of general formula (Al) under conditions of storage or use.
- the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species.
- the catalyst may be formed in situ from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials.
- the active catalyst may be formed in situ in a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generating species, in a suitable solvent.
- the ligand L, or a ligand L-generating species can be mixed with metal M ions present in the substrate or wash liquor to form the active catalyst in situ.
- Suitable ligand L-generating species include metal-free compounds or metal coordination complexes that comprise the ligand L and can be substituted by metal M ions to form the active complex according the formula (Al).
- the complex is a compound of the general formula (Ilia):
- M * represents hydrogen or a metal selected from Ti. V. Co. Zn. Mg. Ca. Sr. Ba. Na. K, and Li:
- X represents a coordinating species; a represents an integer in the range from 1 to 5; b represents an integer in the range from 1 to 4; c represents zero or an integer in the range from 0 to 5; z represents the charge of the compound and is an integer which can be positive, zero or negative;
- L represents a pentadentate ligand of general formula (III) as defined above.
- the ligand L has the general formula (IV):
- R6 is -H. alkyl. - OH or -SH. and R7. R8. R9. RIO are each independently selected from -H. Co-C 2 o-alkyl. heteroaryl-Co-C 2 o-alkyl. alkoxy-Co-C 8 -alkyl and amino- Co-C2o-alkyl.
- More preferred ligands are:
- the bleaching compositions according to the present invention may be used for laundry cleaning, hard surface cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.). As is generally known in the art, bleaching compositions are also employed in waste-water treatment, pulp bleaching during the manufacture of paper, leather manufacture, dye transfer inhibition, food processing, starch bleaching, sterilisation, whitening in oral hygiene preparations and/or contact lens disinfection. In the context of the present invention bleaching should be understood as relating generally to the decolourisation of stains or of other materials attached to or associated with a substrate.
- the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to or otherwise associated with a substrate.
- bleaching is to be understood as being restricted to any bleaching mechanism or process that does not require the presence of light or activation by light.
- photobleaching compositions and processes relying on the use of photobleach catalysts or photobleach activators and the presence of light are excluded from the present invention.
- the level of the catalyst is such that the in-use level is from 0.05 ⁇ M to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 0.5 ⁇ M to 100 ⁇ M. more preferably from 1 ⁇ M to 10 ⁇ M. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp bleaching.
- the aqueous medium has a pH in the range from pH 6 to 13. more preferably from pH 6 to 11, still more preferably from pH 8 to 11, and most preferably from pH 8 to 10, in particular from pH 9 to 10.
- the bleaching composition of the present invention has particular application in detergent formulations, especially for laundry cleaning. Accordingly, in another preferred embodiment, the present invention provides a detergent bleach composition comprising a bleaching composition as defined above and additionally a surface-active material, optionally together with detergency builder.
- the bleach composition according to the present invention may for example contain a surface-active material in an amount of from 10 to 50% by weight.
- the surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof.
- suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents". Volumes 1 and II. by Schwartz. Perry and Berch.
- Typical synthetic anionic surface-actives are usually water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term '"alkyl " ' being used to include the alkyl portion of higher aryl groups.
- suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulfates.
- C 8 -C ⁇ 8 higher alcohols produced, for example, from tallow or coconut oil
- sodium alkyl glyceryl ether sulfates especially those obtained by sulfating higher (C 8 -C ⁇ 8 ) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C -C 2 o) benzene sulfonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulfonates; sodium alkyl glyceryl ether sulfates.
- ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulfates and sulfonates sodium and ammonium salts of sulfuric acid esters of higher (C -C ⁇ 8 ) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulfonates such as those derived by reacting alpha-olefins (C 8 -C 20 ) with sodium bisulfite and those derived by reacting paraffins with SO 2 and Cl 2 and then hydro lysing with a base to produce a random sulfonate: sodium and ammonium (C -C ⁇ 2 ) dialkyl sulfosuccinates; and olefin sulfonates, which term is used to
- nonionic surface-active compounds which may be used, preferably together with the anionic surface-active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6 -C 22 ) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (C 8 -C] 8 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO.
- nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertian 7 amine oxides, long-chain tertian' phosphine oxides and dialkyl sulfoxides.
- Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
- the detergent bleach composition of the invention will preferably comprise from 1 to 15 % wt of anionic surfactant and from 10 to 40 % by weight of nonionic surfactant.
- the detergent active system is free from C 16 -C 1 2 fatty acid soaps.
- the bleach composition of the present invention may also contains a detergency builder, for example in an amount of from about 5 to 80 % by weight, preferably from about 10 to 60 % by weight.
- Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
- Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US-A-4, 144,226 and US-A-4, 146,495.
- alkali metal polyphosphates such as sodium tripolyphosphate
- the alkali metal salts of carboxymethyloxy succinic acid ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid
- polyacetal carboxylates as disclosed in US-A-4, 144,226
- Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
- Examples of calcium ion-exchange builder materials include the various types of water- insoluble crystalline or amorphous aluminosilicates. of which zeolites are the best known representatives, e.g. zeolite A. zeolite B (also known as zeolite P). zeolite C. zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0.384.070.
- compositions of the invention may contain any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or only used in very small amounts.
- Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carbonate. the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyloxy malonate. carboxymethyloxy succinate and water-insoluble crystalline or amorphous aluminosilicate builder materials, each of which can be used as the main builder, either alone or in admixture with minor amounts of other builders or polymers as co-builder.
- the composition contains not more than 5% by weight of a carbonate builder, expressed as sodium carbonate, more preferably not more than 2.5 % by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
- the bleach composition of the present invention can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent compositions.
- these additives include buffers such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkemel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti- redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; stabilisers, such as phosphonic acid derivatives (i.e.
- Dequest® types fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulfate and sodium silicate; and, usually in very small amounts, fluorescent agents; perfumes; enzymes, such as proteases, cellulases, lipases, amylases and oxidases; germicides and colourants.
- Transition metal sequestrants such as EDTA. and phosphonic acid derivatives such as EDTMP (ethylene diamine tetra(methylene phosphonate)) may also be included, in addition to the ligand specified, for example to improve the stability sensitive ingredients such as enzymes, fluorescent agents and perfumes, but provided the composition remains bleaching effective.
- the composition according to the present invention containing the ligand. is preferably substantially, and more preferabh completely, devoid of transition metal sequestrants (other than the ligand).
- the present invention is based on the catalytic bleaching of a substrate b> atmospheric oxygen or air.
- small amounts of hydrogen peroxide or peroxy-based or -generating systems may be included in the composition, if desired. Therefore, by '"substantially devoid of peroxygen bleach or peroxy-based or - generating bleach systems' " is meant that the composition contains from 0 to 50 %. preferably from 0 to 10 %, more preferably from 0 to 5 %, and optimally from 0 to 2 % by molar weight on an oxygen basis, of peroxygen bleach or peroxy-based or - generating bleach systems. Preferably, however, the composition will be wholly devoid of peroxygen bleach or peroxy-based or -generating bleach systems.
- At least 10 %, preferably at least 50 % and optimally at least 90 % of any bleaching of the substrate is effected by oxygen sourced from the air.
- the catalyst may be contacted to the textile fabric in any suitable manner.
- it may be applied in dry form, such as in powder form, or in a liquor that is then dried, for example as an aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning, or a non-aqueous dry cleaning fluid or spray- on aerosol fluid.
- aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning
- a non-aqueous dry cleaning fluid or spray- on aerosol fluid for example as an aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning
- Other suitable means of contacting the catalyst to the textile may be used, as further explained below.
- any suitable textile that is susceptible to bleaching or one that one might wish to subject to bleaching may be used.
- the textile is a laundry fabric or garment.
- the bleaching method of the fourth aspect may be carried out by simply leaving the substrate in contact with the catalyst for a sufficient period of time.
- the catalyst is in an aqueous medium, and the aqueous medium on or containing the substrate is agitated.
- the treated textile is dried, by allowing it to dry under ambient temperature or at elevated temperatures.
- the method according to the fourth aspect is carried out on a laundry fabric using aqueous treatment liquor.
- the treatment may be effected in. or as an adjunct to, an essentially conventional wash cycle for cleaning laundry.
- the treatment is carried out in an aqueous detergent wash liquor.
- the catalyst can be delivered into the wash liquor from a powder, granule, pellet, tablet, block, bar or other such solid form.
- the solid form can comprise a carrier, which can be particulate. sheet-like or comprise a three-dimensional object.
- the carrier can be dispersible or soluble in the wash liquor or may remain substantially intact.
- the catalyst can be delivered into the wash liquor from a paste, gel or liquid concentrate.
- the catalyst used in the method of the fourth aspect makes use of atmospheric oxygen in its bleaching activity. This avoids the requirement that peroxygen bleaches and/or other relatively large quantities of reactive substances need be used in the treatment process. Consequently, only a relatively small quantity of bleach active substance need be employed and this allows dosage routes to be exploited which could previously not be used.
- a composition that is normally used in a washing process such as a pre-treatment, main- wash, conditioning composition or ironing aid
- other means for ensuring that the catalyst is present in the wash liquor may be envisaged.
- the catalyst can be presented in the form of a body from which it is slowly released during the whole or part of the laundry process. Such release can occur over the course of a single wash or over the course of a plurality of washes.
- the catalyst can be released from a carrier substrate used in association with the wash process, e.g. from a body placed in the dispenser drawer of a washing machine, elsewhere in the delivery system or in the drum of the washing machine.
- the carrier can be freely moving or fixed relative to the drum. Such fixing can be achieved by mechanical means, for example by barbs that interact with the drum wall, or employ other forces, for example a magnetic force.
- the catalyst can be presented in the form of a wash additive that preferably is soluble.
- the additive can take any of the physical forms used for wash additives, including powder, granule, pellet, sheet, tablet, block, bar or other such solid form or take the form of a paste, gel or liquid. Dosage of the additive can be unitary or in a quantity determined by the user. While it is envisaged that such additives can be used in the main washing cycle, the use of them in the conditioning or drying cycle is not hereby excluded.
- the present invention is not limited to those circumstances in which a washing machine is employed, but can be applied where washing is performed in some alternative vessel.
- the catalyst can be delivered by means of slow release from the bowl, bucket or other vessel which is being employed, or from any implement which is being employed, such as a brush, bat or dolly, or from any suitable applicator.
- Suitable pre-treatment means for application of the catalyst to the textile material prior to the main wash include sprays, pens, roller-ball devices, bars, soft solid applicator sticks and impregnated cloths or cloths containing microcapsules.
- Such means are well known in the analogous art of deodorant application and/or in spot treatment of textiles.
- Similar means for application are employed in those embodiments where the catalyst is applied after the main washing and/or conditioning steps have been performed, e.g. prior to or after ironing or drying of the cloth.
- the catalyst may be applied using tapes, sheets or sticking plasters coated or impregnated with the substance, or containing microcapsules of the substance.
- the catalyst may for example be incorporated into a drier sheet so as to be activated or released during a tumble-drier cycle, or the substance can be provided in an impregnated or microcapsule-containing sheet so as to be delivered to the textile when ironed.
- alkyl linear and branched Cl-C8-alkyl
- alkenyl C2-C6-alkenyl
- cycloalkyl C3-C8-cycloalkyl.
- alkoxy Cl-C6-alkoxy.
- alkylene selected from the group consisting of: methylene; 1,1 -ethylene; 1,2- ethylene; 1,1-propylidene; 1 ,2-propylene; 1,3-propylene; 2.2-propylidene; butan-2-ol- 1,4-diyl; propan-2-ol-l,3-diyl; 1 ,4-butylene; cyclohexane-l,l-diyl; cyclohexan-l ,2-diyl; cyclohexan-l,3-diyl; cyclohexan- 1,4-diyl; cyclopentane-l,l-diyl; cyclopentan-1.2-diyl; and cyclopentan-l,3-diyl,
- aryl selected from homoaromatic compounds having a molecular weight under 300
- arylene selected from the group consisting of: 1.2-phenylene; 1.3-phenylene: 1.4- phenylene: 1.2-naphtalenylene: 1.3-naphtalenylene: 1.4-naphtalenylene; 2.3- naphtalenylene; l-hydroxy-2,3-phenylene: l-hydrox>-2.4-phenylene: l-hydrox ⁇ -2.5- phenylene: and l-hydroxy-2.6-phenylene.
- heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl: pyrazinyl: triazolyl; pyridazinyl; 1.3.5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl: imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl: indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl,
- heteroarylene selected from the group consisting of: pyridindiyl; quinolindiyl: pyrazodiyl; pyrazoldiyl; triazolediyl; pyrazindiyl; and imidazolediyl.
- heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroarylene
- more specifically preferred are: pyridin-2.3-diyl; pyridin-2,4-diyl; pyridin-2.5-diyl; pyridin-2.6-diyl; pyridin-3.4-diyl; pyridin-3.5-diyl; quinolin-2.3-diyl; quinolin-2.4-diyl; quinolin-2,8-diyl; isoquinolin-1.3-diyl; isoquinolin- 1,4-diyl; pyrazol- 1,3-diyl; pyrazol-3.5-diyl; triazole-3.5-diyl; triazole- 1,3-diyl; pyrazin-2.5-diyl; and imidazole-2.4-diyl,
- heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1.4-piperazinyl: tetrahydrothiophenyl; tetrahydrofuranyl; 1,4,7-triazacyclononanyl; 1.4,8.1 1- tetraazacyclotetradecanyl; 1 ,4,7, 10, 13-pentaazacyclopentadecanyl; 1.4-diaza-7-thia- cyclononanyl; l,4-diaza-7-oxa-cyclononanyl; 1.4,7,10-tetraazacyclododecanyl; 1,4- dioxanyl; 1,4,7-trithia-cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the
- heterocycloalkylene selected from the group consisting of: piperidin-1 ,2-ylene; piperidin-2,6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; 1 ,4-piperazin-2,3- ylene: 1 ,4-piperazin-2.5-ylene; 1.4-piperazin-2.6-ylene: 1.4-piperazin-l.2-ylene: 1.4- piperazin- 1.3 -ylene ; 1.4-piperazin- 1.4-y lene ; tetrahydrothiophen-2.5 -ylene : tetrahydrothiophen-3 ,4-ylene; tetrahydrothiophen-2.3 -ylene ; tetrahydrofuran-2.5 -ylene : tetrahydrofuran-3.4-ylene: tetrahydrofuran-2.3-ylene; pyrrolidin-2.5-ylene:
- each R is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R are Cl- C6-alkyl both R together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring,
- halogen selected from the group consisting of: F; Cl; Br and I, sulfonate: the group -S(O) 2 OR.
- R is selected from: hydrogen: Cl-C6-alkyl: phenyl; Cl-C6-alkyl-C6H5: Li: Na: K: Cs; Mg: and Ca.
- R is selected from: hydrogen: Cl-C6-alkyl: phenyl; Cl-C6-alkyl-C6H5; Li; Na; K: Cs; Mg: and Ca.
- sulfone the group -S(O) 2 R, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5 and amine (to give sulfonamide) selected from the group: - NR'2.
- R is independently selected from: hydrogen; C 1 -C6-alkyl; C 1 -C6- alkyl-C6H5; and phenyl, wherein when both R are Cl-C6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring.
- carboxylate derivative the group -C(O)OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5: Li; Na; K; Cs; Mg; and Ca,
- carbonyl derivative the group -C(O)R, wherein R is selected from: hydrogen; C1-C6- alkyl; phenyl; Cl-C6-alkyl-C6H5 and amine (to give amide) selected from the group: - NR'2, wherein each R' is independently selected from: hydrogen; C 1 -C6-alkyl: C 1 -C6- alkyl-C6H5; and phenyl, wherein when both R' are Cl-C6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring,
- phosphonate the group -P(O)(OR) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca,
- phosphate the group -OP(O)(OR) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca
- phosphine the group -P(R)2- wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5.
- phosphine oxide the group -P(O)R 2 , wherein R is independently selected from: hydrogen: C 1 -C6-alkyl; phenyl: and C 1 -C6-alkyl-C6H5 ; and amine (to give phosphonamidate) selected from the group: -NR'2.
- each R' is independentl y selected from: hydrogen; Cl-C6-alkyl: Cl-C6-alkyl-C6H5; and phenyl. wherein when both R' are Cl-C6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring.
- alkyl linear and branched C 1 -C6-alkyl
- alkenyl C3-C6-alkenyl
- cycloalkyl C6-C8-cycloalkyl.
- alkoxy Cl-C4-alkoxy
- alkylene selected from the group consisting of: methylene; 1.2-ethylene; 1.3- propylene; butan-2-ol- 1,4-diyl; 1,4-butylene; cyclohexane-l,l-diyl; cyclohexan-l,2-diyl; cyclohexan- 1,4-diyl; cyclopentane-l,l-diyl; and cyclopentan-l,2-diyl,
- aryl selected from group consisting of: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl,
- arylene selected from the group consisting of: 1,2-phenylene; 1,3-phenylene; 1,4- phenylene; 1 ,2-naphtalenylene; 1,4-naphtalenylene; 2,3-naphtalenylene and 1-hydroxy- 2,6-phenylene
- heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl: quinolinyl: pyrazolyl; triazolyl; isoquinolinyl imidazolyl; and oxazolidinyl.
- the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl.
- heteroarylene selected from the group consisting of: pyridin-2.3-diyl; pyridin-2.4-diyl: pyridin-2,6-diyl; pyridin-3,5-diyl; quinolin-2,3-diyl; quinolin-2.4-diyl; isoquinolin-1.3- diyl; isoquinolin- 1,4-diyl; pyrazol-3,5-diyl; and imidazole-2.4-diyl.
- heterocycloalkyl selected from the group consisting of: pyrrolidinyl; mo holinyl; piperidinyl; piperidinyl; 1,4-piperazinyl; tetrahydrofuranyl; 1.4.7-triazacyclononanyl; 1,4.8,1 1 -tetraazacyclotetradecanyl; 1,4,7,10,13-pentaazacyclopentadecanyl; 1.4.7.10- tetraazacyclododecanyl; and piperazinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl.
- heterocycloalkylene selected from the group consisting of: piperidin-2.6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; 1.4-piperazin-2.3-ylene; 1 ,4-piperazin- 2,6-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrofuran- 2,5-ylene; tetrahydrofuran-3 ,4-ylene; pyrrolidin-2,5-ylene; pyrrolidin-2,2-ylidene; 1,4,7- triazacyclonon-l,4-ylene; 1.4,7-triazacyclonon-2.3-ylene; 1.4,7-triazacyclonon-2.2- ylidene; 1,4,8,11-tetraazacyclotetradec- 1,4-ylene; 1,4,8.1 1-tetraazacyclotetradec
- halogen selected from the group consisting of: F and Cl.
- sulfonate the group -S(O) 2 OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; Na; K; Mg; and Ca,
- R is selected from: hydrogen: Cl-C6-alkyl; Na; K; Mg; and Ca,
- sulfone the group -S(O) 2 R, wherein R is selected from: hydrogen; Cl -C6-alkyl; benzyl and amine selected from the group: -NR'2. wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl.
- carboxylate derivative the group -C(O)OR.
- R is selected from hydrogen; Na; K; Mg; Ca; Cl-C6-alkyl; and benzyl,
- carbonyl derivative the group: -C(O)R, wherein R is selected from: hydrogen; C1-C6- alkyl; benzyl and amine selected from the group: -NR'2. wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl,
- phosphonate the group -P(O)(OR) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca,
- phosphate the group -OP(O)(OR) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca,
- phosphine the group -P(R) 2 , wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, phosphine oxide: the group -P(O)R 2 .
- R is independently selected from: hydrogen: Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2.
- each R' is independently selected from: hydrogen; Cl-C6-alkyl: and benzyl.
- Compound 16 N-methyl-N,N',N'-tris(pyridin-2-ylmethyl)-ethylenediamine + Fe(ClO 4 ) 2 .
- Compound 48 N,N,N'-tris( 1 -methyl-benzimidazol-2-yl)-N'-methyl-ethylenediamine
- Compound 49 N,N,N'-tris(l-methyl-benzimidazol-2-yl)-N'-methyl-ethylenediamine + Co(ClO 4 ) 2 . 6H 2 O
- Compound 50 N,N,N'-tris(l -methyl-benzimidazol-2-yl)-N'-methyl-ethylenediamine + Fe(ClO 4 ) 2 . 6H 2 O
- Compound 51 N.N.N'-tris(l-methyl-benzimidazol-2-yl)-N'-methyl-ethylenediamine -r Mn(ClO 4 ) 2 . 6H 2 O
- N-ethyl amino acetonitrile This synthesis was performed analogously to the synthesis reported for N-benzyl amino acetonitrile. However, detection was done by dipping the TLC plate in a solution of KMnO and heating the plate until bright spots appeared. Starting from ethylamine (2.25 g, 50 mmol), pure N-ethyl amino acetonitrile (0.68 g, 8.1 mmol, 16 %) was obtained as a slightly yellow oil.
- N-methyl ethylene- 1.2-diamine (502 mg, 6.8 mmol) and additional ⁇ aOH (5 ⁇ , 10 mL) were added.
- the reaction mixture was stirred at room temperature for 45 hours.
- the mixture was poured into water (200 mL). and the pH checked (> 14, otherwise addition of ⁇ aOH (aq. 5 ⁇ )).
- the reaction mixture was extracted with dichloromethane (3 or 4 x 50 mL. until no product could be detected by TLC).
- the combined organic phases were dried and the solvent removed in vacuo. Purification was enforced as described before, yielding ⁇ /T -methyl-N,N.N-tris(3- methylpyridin-2-ylmethyl)ethylene-l,2-diamine as a slightly yellow oil.
- Picolyl chloride (2.1 g. 12.8 mmol) was dissolved in a 0.8 ml water and 3 ml 5N NaOH (15 mmol) was added. The resulting mixture was added to N-hydroxyethyl-diethylene amine (0.4 g. 3.85 mmol) followed by 4 ml 5N NaOH (20 mmol) and cetyltrimethylammonium bromide (20 mg) and dichloromethane (1 ml) and the mixture was stirred at 20 C. After 4 days the mixture was extracted with an ether/toluene mix and the ether/toluene layer was washed with saturated aqueous NaCl.
- the ligand compound 14 was prepared according to Bernal, Ivan; Jensen, Inge Margrethe; Jensen, Kenneth B.; McKenzie, Christine J.; Toftlund, Hans; Tuchagues, Jean-Pierre; J.Chem.Soc.Dalton Trans.; 22; 1995; 3667-3676.
- N-ethyl-N.N',N'-tris(3-methyl-pyridin-2-ylmethyl)-ethylenediamine was synthesised analogously to the synthesis for L. Starting from 2-hydroxymethyl-3-methyl pyridine
- the pH of the aqueous phase was adjusted to >11 by the addition of sodium hydroxide solution (5 N).
- the aqueous phase was extracted with dichloromethane (3 x 50 mL).
- the combined organic phases were evaporated in vacuo and subsequently stripped with dichloromethane.
- the change in colour was measured immediately after drying with a Linotype-Hell scanner (ex Linotype).
- the change in colour is expressed as the ⁇ E value.
- the measured colour difference ( ⁇ E) between the washed cloth and the unwashed cloth is defined as follows:
- ⁇ E [( ⁇ L) 2 +( ⁇ a) 2 +( ⁇ b) 2 ]' /2
- ⁇ L is a measure for the difference in darkness between the washed and unwashed test cloth; ⁇ a and ⁇ b are measures for the difference in redness and yellowness respectively between both cloths.
- CIE Commission International de l'Eclairage
Abstract
Description
Claims
Priority Applications (1)
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AU41091/00A AU4109100A (en) | 1999-04-01 | 2000-03-22 | Composition and method for bleaching a substrate |
Applications Claiming Priority (10)
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GBGB9907713.3A GB9907713D0 (en) | 1999-04-01 | 1999-04-01 | Method of treating a textile |
GB9907713.3 | 1999-04-01 | ||
GB9907714.1 | 1999-04-01 | ||
GBGB9907714.1A GB9907714D0 (en) | 1999-04-01 | 1999-04-01 | Composition and method for bleaching a substrate |
PCT/GB1999/002878 WO2000012808A1 (en) | 1998-09-01 | 1999-09-01 | Method of treating a textile |
PCT/GB1999/002876 WO2000012667A1 (en) | 1998-09-01 | 1999-09-01 | Composition and method for bleaching a substrate |
GBPCT/GB99/02876 | 1999-09-01 | ||
GBPCT/GB99/02878 | 1999-09-01 | ||
GB0004850A GB0004850D0 (en) | 2000-02-29 | 2000-02-29 | Compositon and method for bleaching a substrate |
GB0004858.7 | 2000-02-29 |
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WO2002066592A1 (en) * | 2001-02-16 | 2002-08-29 | Unilever Plc | Bleaching composition of enhanced stability and a process for making such a composition |
WO2002077145A1 (en) * | 2001-02-05 | 2002-10-03 | Unilever Plc | Composition and method for bleachin g a substrate |
WO2002081613A1 (en) * | 2001-04-06 | 2002-10-17 | Unilever Plc | Composition and method for bleaching a substrate |
US6518231B2 (en) | 2000-12-18 | 2003-02-11 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Enhancement of air bleaching catalysts |
WO2003097780A1 (en) * | 2002-05-20 | 2003-11-27 | Unilever N.V. | Enzymatic detergent compositions |
WO2003104377A1 (en) * | 2002-06-06 | 2003-12-18 | Unilever N.V. | Enhancement of bleaching catalysts |
WO2004000985A1 (en) * | 2002-06-21 | 2003-12-31 | Degussa Ag | Use of transition metal complexes as a bleaching catalyst |
WO2004039933A1 (en) * | 2002-10-29 | 2004-05-13 | Ciba Specialty Chemicals Holding Inc. | Use of metal complex compounds as catalysts for oxidation using molecular oxygen or air |
WO2004039932A1 (en) * | 2002-10-30 | 2004-05-13 | Reckitt Benckiser N.V. | Use of metal complex compounds as oxidation catalysts |
WO2004039934A1 (en) * | 2002-10-30 | 2004-05-13 | Ciba Specialty Chemicals Holding Inc. | Use of metal complex compounds as oxidation catalysts |
WO2004104155A1 (en) * | 2003-05-21 | 2004-12-02 | Ciba Specialty Chemicals Holding Inc. | Stable particulate composition comprising bleach catalysts |
WO2005061688A1 (en) * | 2003-12-20 | 2005-07-07 | Reckitt Benckiser N.V. | Use of metal complex compounds as oxidation catalysts |
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US8945671B2 (en) | 2007-12-19 | 2015-02-03 | Evonik Treibacher Gmbh | Method for producing encapsulated sodium percarbonate particles |
EP3795665A1 (en) * | 2019-09-20 | 2021-03-24 | Henkel AG & Co. KGaA | Non-enzymatic removal of proteinaceous soils |
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US6340661B1 (en) | 2000-03-01 | 2002-01-22 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Bleaching and dye transfer inhibiting composition and method for laundry fabrics |
WO2001064824A1 (en) * | 2000-03-01 | 2001-09-07 | Unilever Plc | Bleaching and dye transfer inhibiting composition and method for stain bleaching of laundry fabrics |
US6518231B2 (en) | 2000-12-18 | 2003-02-11 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Enhancement of air bleaching catalysts |
WO2002077145A1 (en) * | 2001-02-05 | 2002-10-03 | Unilever Plc | Composition and method for bleachin g a substrate |
US6696403B2 (en) | 2001-02-05 | 2004-02-24 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Composition and method for bleaching a substrate |
US6720299B2 (en) | 2001-02-16 | 2004-04-13 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Bleaching composition of enhanced stability and a process for making such a composition |
WO2002066592A1 (en) * | 2001-02-16 | 2002-08-29 | Unilever Plc | Bleaching composition of enhanced stability and a process for making such a composition |
AU2002237288B2 (en) * | 2001-02-16 | 2004-10-14 | Unilever Plc | Bleaching composition of enhanced stability and a process for making such a composition |
WO2002081613A1 (en) * | 2001-04-06 | 2002-10-17 | Unilever Plc | Composition and method for bleaching a substrate |
WO2003097780A1 (en) * | 2002-05-20 | 2003-11-27 | Unilever N.V. | Enzymatic detergent compositions |
WO2003104377A1 (en) * | 2002-06-06 | 2003-12-18 | Unilever N.V. | Enhancement of bleaching catalysts |
WO2004000985A1 (en) * | 2002-06-21 | 2003-12-31 | Degussa Ag | Use of transition metal complexes as a bleaching catalyst |
WO2004039933A1 (en) * | 2002-10-29 | 2004-05-13 | Ciba Specialty Chemicals Holding Inc. | Use of metal complex compounds as catalysts for oxidation using molecular oxygen or air |
US7291584B2 (en) | 2002-10-30 | 2007-11-06 | Ciba Specialty Chemicals Corporation | Use of metal complex compounds as oxidation catalysts |
WO2004039932A1 (en) * | 2002-10-30 | 2004-05-13 | Reckitt Benckiser N.V. | Use of metal complex compounds as oxidation catalysts |
WO2004039934A1 (en) * | 2002-10-30 | 2004-05-13 | Ciba Specialty Chemicals Holding Inc. | Use of metal complex compounds as oxidation catalysts |
US7612010B2 (en) | 2002-10-30 | 2009-11-03 | Ciba Specialty Chemicals Corp. | Use of metal complex compounds as oxidation catalysts |
JP2006504517A (en) * | 2002-10-30 | 2006-02-09 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Use of metal complex compounds as oxidation catalysts |
US7138363B2 (en) | 2002-10-30 | 2006-11-21 | Ciba Specialty Chemicals Corporation | Use of metal complex compounds as oxidation catalysts |
WO2004104155A1 (en) * | 2003-05-21 | 2004-12-02 | Ciba Specialty Chemicals Holding Inc. | Stable particulate composition comprising bleach catalysts |
AU2004241037B2 (en) * | 2003-05-21 | 2010-07-08 | Basf Se | Stable particulate composition comprising bleach catalysts |
WO2005061688A1 (en) * | 2003-12-20 | 2005-07-07 | Reckitt Benckiser N.V. | Use of metal complex compounds as oxidation catalysts |
US7956027B2 (en) | 2006-07-27 | 2011-06-07 | Evonik Degussa Gmbh | Coated sodium percarbonate particles |
US8153576B2 (en) | 2006-07-27 | 2012-04-10 | Evonik Degussa Gmbh | Coated sodium percarbonate particles |
US8658590B2 (en) | 2006-07-27 | 2014-02-25 | Evonik Degussa Gmbh | Coated sodium percarbonate particles |
US8945671B2 (en) | 2007-12-19 | 2015-02-03 | Evonik Treibacher Gmbh | Method for producing encapsulated sodium percarbonate particles |
EP3795665A1 (en) * | 2019-09-20 | 2021-03-24 | Henkel AG & Co. KGaA | Non-enzymatic removal of proteinaceous soils |
US20210087496A1 (en) * | 2019-09-20 | 2021-03-25 | Henkel Ag & Co. Kgaa | Non-Enzymatic Removal Of Proteinaceous Soils |
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