WO2004039934A1 - Use of metal complex compounds as oxidation catalysts - Google Patents
Use of metal complex compounds as oxidation catalysts Download PDFInfo
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- WO2004039934A1 WO2004039934A1 PCT/EP2003/011636 EP0311636W WO2004039934A1 WO 2004039934 A1 WO2004039934 A1 WO 2004039934A1 EP 0311636 W EP0311636 W EP 0311636W WO 2004039934 A1 WO2004039934 A1 WO 2004039934A1
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- 0 CC(CC*)*1CC[N+]CCC1 Chemical compound CC(CC*)*1CC[N+]CCC1 0.000 description 4
- ZIZZXDMKZGRVOJ-UHFFFAOYSA-N CCOC(CC(c1nccc(Cl)c1)=O)=O Chemical compound CCOC(CC(c1nccc(Cl)c1)=O)=O ZIZZXDMKZGRVOJ-UHFFFAOYSA-N 0.000 description 1
- DYEZRXLVZMZHQT-UHFFFAOYSA-N N#Cc1cc(Cl)ccn1 Chemical compound N#Cc1cc(Cl)ccn1 DYEZRXLVZMZHQT-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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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
- C11D3/16—Organic compounds
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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
- C11D3/16—Organic compounds
- C11D3/168—Organometallic compounds or orgometallic complexes
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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
Definitions
- the present invention relates to the use, as oxidation catalysts, of metal complex compounds having pyrimidine or triazinebispyrimidine ligands or mixtures of such ligands.
- the present invention relates also to formulations comprising such metal complex compounds, to novel metal complex compounds and to novel ligands.
- the metal complex compounds are used especially for enhancing the action of peroxides, for example in the treatment of textile material, without at the same time causing any appreciable damage to fibres and dyeings.
- the metal complex 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.
- 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 H 2 O 2 . In that manner it is possible for the bleaching effect, which is unsatisfactory at lower temperatures, of H 2 O 2 or precursors that release H 2 O 2 and of other peroxo compounds, to be increased.
- the invention accordingly relates to the use, as a catalyst for oxidation reactions, of at least one metal complex of formula (1 )
- Me manganese, titanium, iron, cobalt, nickel or copper
- X is a coordinating or bridging radical
- n and m are each independently of the other an integer having a value of from 1 to 8
- p is an integer having a value of from 0 to 32
- z is the charge of the metal complex
- Y is a counter-ion
- q z/(charge of Y)
- L is a ligand of formula (2)
- Q is N or CR 10 .
- e, R7, Re, R9 and R- ⁇ 0 are each independently of the others hydrogen; unsubstituted or substituted CrCi ⁇ alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro; -COORn or -SO3R.1 wherein
- Rn is in each case hydrogen, a cation or unsubstituted or substituted CrC 18 alkyl or unsubstituted or substituted aryl; -SR 12 , -SO2R 12 or -OR 12 wherein
- R 12 is in each case hydrogen or unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl; -NR 13 R 1 ; -(C 1 -C 6 alkylene)-NR 13 R ⁇ ; -N ⁇ R ⁇ 3 R ⁇ Ri5; -(C 1 -C 6 alkylene)-N e R 1 3Ri 4 Ri 5 ; -N(Ri2)-(C 1 -C 6 alkylene)-NR 13 R ⁇ ;
- R 12 is as defined above and
- R 13 , R and R 15 are each independently of the other(s) hydrogen or unsubstituted or substituted CrC 18 alkyl or unsubstituted or substituted aryl, or
- R 13 and R 14 together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms.
- a specific use as a catalyst is in relation to oxidation using molecular oxygen and/or air.
- Suitable substituents for the alkyl groups, aryl groups, alkylene groups or 5-, 6- or 7- membered rings are especially C ⁇ -C alkyl; d-C alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-CrC alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino; phenyl; phenoxy or naphthyloxy.
- the CrC ⁇ 8 alkyl radicals mentioned for the compounds of formula (2) are, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl.
- the mentioned alkyl radicals may be unsubstituted or substituted e.g.
- aryl radicals that come into consideration for the compounds of formula (2) are phenyl or naphthyl each unsubstituted or substituted by CrC 4 alkyl, CrC 4 alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N.N-di-Crdalkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N- naphthylamino, wherein the amino groups may be quaternised, phenyl, phenoxy or by naphthyloxy.
- Preferred substituents are CrC 4 alkyl, CrC 4 alkoxy, phenyl and hydroxy. Special preference is given to the corresponding phenyl radicals.
- the d-C ⁇ alkylene groups mentioned for the compounds of formula (2) are, for example, straight-chain or branched alkylene radicals, such as methylene, ethylene, n-propylene or n-butylene. C C 4 Alkylene groups are preferred.
- the alkylene radicals mentioned may be unsubstituted or substituted, for example by hydroxy or C ⁇ -C alkoxy.
- halogen is preferably chlorine, bromine or fluorine, with special preference being given to chlorine.
- Examples of cations that come into consideration for compounds of formulae (1 ) and (2) include alkali metal cations, such as lithium, potassium and especially sodium, alkaline earth metal cations, such as magnesium and calcium, and ammonium cations.
- alkali metal cations, especially sodium are preferred.
- Suitable metal ions for Me for the compounds of formula (1 ) are, for example, manganese in oxidation states ll-V, titanium in oxidation states III and IV, iron in oxidation states I to IV, cobalt in oxidation states I to III, nickel in oxidation states I to III and copper in oxidation states I to III, with special preference being given to manganese, especially manganese in oxidation states II to IV, preferably in oxidation state II. Also of interest are titanium IV, iron II- IV, cobalt ll-lll, nickel ll-lll and copper ll-lll, especially iron ll-IV.
- radical X for the compounds of formula (1) there come into consideration, for example, CH 3 CN; H 2 O; F; CI " ; Br ' ; HOO ' ; O 2 2' ; O 2' ; R ⁇ 6 COO " ; R 16 O " ; LMeO ' and LMeOO ' , wherein R 16 is hydrogen, -SO 3 C ⁇ -C alkyl or unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl, and CrC ⁇ 8 alkyl, aryl, L and Me have the definitions and preferred meanings given hereinabove and hereinbelow.
- R ⁇ 6 is hydrogen; C C 4 alkyl; sulfophenyl or phenyl, especially hydrogen.
- R 17 as CrC ⁇ 8 alkyl or aryl has the definitions and preferred meanings given hereinabove and hereinbelow.
- R 17 is hydrogen; C C 4 alkyl; phenyl or sulfophenyl, especially hydrogen or 4-sulfophenyl.
- the charge of the counter-ion Y is accordingly preferably 1 - or 2-, especially 1-.
- Y can also be a customary organic counter-ion, for example citrate, oxalate or tartrate.
- n is preferably an integer having a value of from 1 to 4, preferably 1 or 2 and especially 1.
- m is preferably an integer having a value of 1 or 2, especially 1.
- p is preferably an integer having a value of from 0 to 4, especially 2.
- z is preferably an integer having a value of from 8- to 8+, especially from 4- to 4+ and especially preferably from 0 to 4+. z is more especially the number 0.
- q is preferably an integer from 0 to 8, especially from 0 to 4, and is especially preferably the number 0.
- Rn in compounds of formula (2) is preferably hydrogen, a cation, C ⁇ -C 12 al yl, unsubstituted phenyl or phenyl substituted as indicated above.
- Rn is hydrogen, an alkali metal cation, alkaline earth metal cation or ammonium cation, C 1 -C 4 alkyl or phenyl, especially hydrogen or an alkali metal cation, alkaline earth metal cation or ammonium cation.
- R 12 in compounds of formula (2) is preferably hydrogen, C ⁇ -C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- R ⁇ 2 is hydrogen, d-C 4 alkyl or phenyl, more especially hydrogen or CrC 4 alkyl, preferably hydrogen.
- Examples of the radical of formula -OR ⁇ 2 that may be mentioned are hydroxy and d-C 4 alkoxy, such as methoxy and especially ethoxy.
- R 13 and R 4 in compounds of formula (2) together with the nitrogen atom linking them, form a 5-, 6- or 7-membered ring, that ring is preferably an unsubstituted or d-dalkyl- substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring, wherein the amino groups may be quaternised, in which case preferably the nitrogen atoms that are not bonded directly to one of the three rings A, B or C are quaternised.
- the piperazine ring may, for example, be substituted by one or two unsubstituted d-C alkyl and/or substituted d-C alkyl at the nitrogen atom not bonded to the pyridine ring.
- R-, 3 , R 14 and R 1S are preferably hydrogen, unsubstituted or hydroxy-substituted C ⁇ -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- Special preference is given to hydrogen, unsubstituted or hydroxy-substituted C ⁇ -C 4 alkyl or unsubstituted or hydroxy-substituted phenyl, especially hydrogen or unsubstituted or hydroxy-substituted d-C alkyl, preferably hydrogen.
- R 5 in L of formula (2) is preferably d-C 12 alkyl; phenyl unsubstituted or substituted by d-C 4 alkyl, d-C alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or by naphthyloxy; cyano; halogen; nitro; -COORn or -SO3R 11 wherein R ⁇ is in each case hydrogen, a cation, C ⁇ -C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above; -SR 12 , -SO 2 R 12 or -OR 12 wherein R 12 is in each case hydrogen, d
- R 5 in L of formula (2) is especially preferably phenyl unsubstituted or substituted by d-dalkyl, d-C 4 alkoxy, halogen, phenyl or by hydroxy; cyano; nitro; -COORn or -SO3R1 1 wherein Rn is in each case hydrogen, a cation, d-C 4 alkyl or phenyl; -SR 1 2, -SO 2 R.
- R 12 is in each case hydrogen, d-C 4 alkyl or phenyl; -N(CH 3 )-NH 2 or -NH-NH 2 ; amino; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or an unsubstituted or d-C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- R 5 in L of formula (2) is very especially preferably d-C 4 alkoxy; hydroxy; phenyl unsubstituted or substituted by d-dalkyl, d-C 4 alkoxy, phenyl or by hydroxy; hydrazine; amino; N-mono- or N,N-di-d-C alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or an unsubstituted or C ⁇ -C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- radicals R 5 in L of formula (2) there are especially important d-dalkoxy; hydroxy; hydrazine; amino; N-mono- or N,N-di-d-C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; and an unsubstituted or d-C alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- radicals R 5 in L of formula (2) there are very especially important d-C alkoxy; hydroxy; N-mono- or N,N-di-d-C 4 alkylamino substituted by hydroxy in the alkyl moiety; and an unsubstituted or d-dalkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring. Of those, hydroxy is of special interest.
- R 5 The preferred meanings given above for R 5 apply also to Ri, R 2 , R 3 , R , Re, R7, Re, g and R 1 0 in L of formula (2), but those radicals may additionally be hydrogen.
- R ⁇ R 2 , R 3 , R 4 , R 6 , R 7 , R 8> Rg and R 10 in L of formula (2) are hydrogen and R 5 in L of formula (2) is a radical other than hydrogen having the definition and preferred meanings indicated above.
- Ri, R 2 , R , R 6 , R 8 , Rg and R10 in L of formula (2) are hydrogen and R 3 , R 5 and R 7 in L of formula (2) are radicals other than hydrogen, for each of which the definition and preferred meanings indicated above for R 5 apply.
- Preferred as ligands L are those of formula (3a) and/or (3b)
- ligands L are those of formula (3a) and/or (3b)
- R's is d-dalkoxy; hydroxy; N-mono- or N.N-di-d-dalkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or -NR ⁇ 3 R ⁇ ; -(d-C 6 alkylene)-NR 13 R ⁇ ;
- R 12 is hydrogen; d-C ⁇ 2 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-C ⁇ -dalkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and
- R 13 and R ⁇ 4 are each independently of the other hydrogen, unsubstituted or hydroxy-substituted C ⁇ -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or
- R 13 and R ⁇ 4 together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted C ⁇ -C 4 alkyl and/or substituted d- dalkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring, and R' 3 and R' 7 are each independently of the other hydrogen; d-C 4 alkoxy; hydroxy; N-mono- or N.N-di-d-dalkylamino substituted by hydroxy in the alkyl moiety; or -NR 13 R ⁇ 4 ; -(C ⁇ -Cealkylene)-NR ⁇ 3 R 14 ; -N(R 12 )-(C 1 -C 6 alkylene)-NR 1 3R ⁇ 4 ; -N[(C ⁇ -C 6 alkylene)-NR 13
- R ⁇ 2 is hydrogen; d-C ⁇ 2 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-C ⁇ -C 4 alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and
- R 13 and R 14 are each independently of the other hydrogen; unsubstituted or hydroxy-substituted d-C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or
- R 13 and R ⁇ 4 together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted d-C 4 alkyl and/or substituted d-C 4 alkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- An embodiment of the invention to which preference is likewise given is the use, as a catalyst for oxidation reactions, of at least one metal complex compound of formula (1 ')
- Me is manganese, titanium, iron, cobalt, nickel or copper
- X is a coordinating or bridging radical
- n and m are each independently of the other an integer having a value of from 1 to 8
- p is an integer having a value of from 0 to 32
- z is the charge of the metal complex
- Y is a counter-ion
- q z/(charge of Y)
- Q is N or CR 10 , Ri, 2, R3, R 4 , Rs, Re, R7, Re. g and R10 are each independently of the others hydrogen; unsubstituted or substituted d-C 18 alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro; -COORn or -SO 3 Rn wherein
- Rn is in each case hydrogen, a cation or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl; -SR ⁇ 2 , -SO 2 R 12 or -OR 12 wherein
- R 12 is in each case hydrogen or unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl; -NR 13 R ⁇ 4 ; -(d-C 6 alkylene)-NR 13 R 14 ; -N ® R 13 R 14 Ri5;
- R 12 is as defined above and
- R 13 > R ⁇ and R15 are each independently of the other(s) hydrogen or unsubstituted or substituted d-C 18 alkyl or unsubstituted or substituted aryl, or
- R 13 and R 14 together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms, with the proviso that at least one of the substituents Ri to R 1 0 contains a quaternised nitrogen atom that is not bonded directly to one of the three rings A, B and/or C.
- Suitable substituents for the alkyl groups, aryl groups, alkylene groups or 5-, 6- or 7- membered rings are especially d-C 4 alkyl; d-dalkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino; phenyl; phenoxy and naphthyloxy.
- the C ⁇ -C ⁇ 8 alkyl radicals mentioned for the compounds of formula (2') are, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl.
- the mentioned alkyl radicals may be unsubstituted or substituted e.g.
- aryl radicals that come into consideration for the compounds of formula (2') are phenyl or naphthyl each unsubstituted or substituted by d-C 4 alkyl, d-C alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N.N-di-d-dalkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N- naphthylamino, wherein the amino groups may be quaternised, phenyl, phenoxy or by naphthyloxy.
- Preferred substituents are C ⁇ -C alkyl, C C alkoxy, phenyl and hydroxy. Special preference is given to the corresponding phenyl radicals.
- the d-C 6 alkylene groups mentioned for the compounds of formula (2') are, for example, straight-chain or branched alkylene radicals, such as methylene, ethylene, n-propylene or n-butylene.
- d-C 4 Alkylene groups are preferred.
- the alkylene radicals mentioned may be unsubstituted or substituted, for example by hydroxy or C ⁇ -C 4 alkoxy.
- halogen is preferably chlorine, bromine or fluorine, with special preference being given to chlorine.
- Examples of cations that come into consideration for compounds of formulae (1 ') and (2') include alkali metal cations, such as lithium, potassium and especially sodium, alkaline earth metal cations, such as magnesium and calcium, and ammonium cations.
- alkali metal cations, especially sodium are preferred.
- Suitable metal ions for Me for the compounds of formula (1') are, for example, manganese in oxidation states ll-V, titanium in oxidation states III and IV, iron in oxidation states I to IV, cobalt in oxidation states I to III, nickel in oxidation states I to III and copper in oxidation states I to III, with special preference being given to manganese, especially manganese in oxidation states II to IV, preferably in oxidation state II. Also of interest are titanium IV, iron ll-IV, cobalt ll-lll, nickel ll-lll and copper ll-lll, especially iron ll-IV.
- radical X for the compounds of formula (1 ') there come into consideration, for example, CH 3 CN, H 2 O, F, CI ' , Br ' , HOO " , O 2 2" , O 2" , RieCOO " , R ⁇ 6 O “ , LMeO ' and LMeOO " , wherein R ⁇ 6 is hydrogen, -SO 3 C ⁇ -C 4 alkyl or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl, and d-C ⁇ 8 alkyl, aryl, L and Me have the definitions and preferred meanings given hereinabove and hereinbelow.
- R ⁇ 6 is hydrogen; d-C 4 alkyl; sulfophenyl or phenyl, especially hydrogen.
- counter-ion Y for the compounds of formula (1 ') there come into consideration, for example, R 17 COO “ , CIO 4 ' , BF 4 " , PF ⁇ “ , R.7SO3 ' , Ri7SO 4 “ , SO 4 2" , NO 3 " , F, CI " , Br “ and I ' , wherein R 17 is hydrogen or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl.
- R 17 as d-C 18 alkyl or aryl has the definitions and preferred meanings given hereinabove and hereinbelow. Especially preferably, R 17 is hydrogen; d-C 4 alkyl; phenyl or sulfophenyl, especially hydrogen or 4-sulfophenyl.
- the charge of the counter-ion Y is accordingly preferably 1 - or 2-, especially 1 -.
- Y can also be a customary organic counter-ion, for example citrate, oxalate or tartrate.
- n is preferably an integer having a value of from 1 to 4, preferably 1 or 2 and especially 1.
- m is preferably an integer having a value of 1 or 2, especially 1.
- p is preferably an integer having a value of from 0 to 4, especially 2.
- z is preferably an integer having a value of from 8- to 8+, especially from 4- to 4+ and especially preferably from 0 to 4+. z is more especially the number 0.
- q is preferably an integer from 0 to 8, especially from 0 to 4, and is especially preferably the number 0.
- Rn in compounds of formula (2') is preferably hydrogen, a cation, d-C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- Rn is hydrogen, an alkali metal cation, alkaline earth metal cation or ammonium cation, d-C 4 alkyl or phenyl, especially hydrogen or an alkali metal cation, alkaline earth metal cation or ammonium cation.
- R 12 in compounds of formula (2') is preferably hydrogen, CrC 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- R 12 is hydrogen, C ⁇ -C 4 alkyl or phenyl, especially hydrogen or C 1 -C 4 alkyl, preferably hydrogen.
- Examples of the radical of formula -OR12 that may be mentioned are hydroxy and d-C 4 alkoxy, such as methoxy and especially ethoxy.
- R 1 3 and R 14 in compounds of formula (2') together with the nitrogen atom linking them, form a 5-, 6- or 7-membered ring, that ring is preferably an unsubstituted or d-C 4 alkyl- substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring, wherein the amino groups may be quaternised, in which case preferably the nitrogen atoms that are not bonded directly to one of the three rings A, B or C are quaternised.
- the piperazine ring may, for example, be substituted by one or two unsubstituted d-C 4 alkyl and/or substituted Ci-dalkyl at the nitrogen atom not bonded to the pyridine ring.
- R 13 , R 14 and R 1S are preferably hydrogen, unsubstituted or hydroxy-substituted d-C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above. Special preference is given to hydrogen, unsubstituted or hydroxy-substituted d-C 4 alkyl, or phenyl, especially hydrogen or unsubstituted or hydroxy-substituted d-C alkyl, preferably hydrogen.
- R 5 is preferably phenyl unsubstituted or substituted by d-C 4 alkyl, d-C 4 alkoxy, halogen, phenyl or by hydroxy; cyano; nitro; -COOR 11 or -SO 3 Rn wherein Rn is in each case hydrogen, a cation, d-C 4 alkyl or phenyl; -SR ⁇ 2 , -SO 2 Ri 2 or -ORi 2 wherein R 12 is in each case hydrogen, d-C 4 alkyl or phenyl; -N(CH 3 )-NH 2 or -NH-NH 2 ; amino; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms not bonded to one of the three rings A, B or C, may be
- Rs in L' of formula (2') is very especially d-dalkoxy; hydroxy; phenyl unsubstituted or substituted by d-dalkyl, d-C alkoxy, phenyl or by hydroxy; hydrazine; amino; N-mono- or N,N-di-d-C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms not bonded to one of the three rings A, B or C, may be quaternised; or a pyrrolidine, piperidine, morpholine or azepane ring unsubstituted or substituted by one or two unsubstituted d-C 4 alkyl and/or substituted d-dalkyl, wherein the nitrogen atom may be quaternised;
- ring, the alkylene group and the two alkyl groups may additionally independently from each other be substituted.
- radicals R s in L' of formula (2') there are especially important d-C 4 alkoxy; hydroxy; hydrazine; amino; N-mono- or N.N-di-d-dalkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms not bonded to one of the three rings A, B or C, may be quaternised; or a pyrrolidine, piperidine, piperazine, morpholine or azepane ring unsubstituted or substituted by at least one d-C 4 alkyl, wherein the nitrogen atoms may be quaternised.
- ring, the alkylene group and the two alkyl groups may additionally independently from each other substituted.
- radicals R 5 in L' of formula (2') there are especially important d-C 4 alkoxy; hydroxy; N-mono- or N,N-di-C ⁇ -C 4 alkylamino substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms not bonded to one of the three rings A, B or C, may be quaternised; or a pyrrolidine, piperidine, morpholine or azepane ring unsubstituted or substituted by at least one d-dalkyl, wherein the amino groups may be quaternised.
- radical R 5 in L' of formula (2') mention may be made especially of -OH; /— ⁇ ⁇ + ,CH 3
- hydroxy is of special interest.
- R 5 in U of formula (2') applies also to R 1( R 2 , R 3 , R 4 , Re > R7.
- Rs, Rg and R 1 0 in L' of formula (2') may additionally be hydrogen.
- R 1 ( R 2 , R 3 , R 4 , R 6 , R , R 8 , 9 and R 10 in U of formula (2') are hydrogen and R s in L' of formula (2') is a radical other than hydrogen having the definition and preferred meanings indicated above.
- R 1 f R 2 , R 3 , R , R 6 , R 7 , R 8 , R 9 and R 10 in L' of formula (2') are hydrogen and R 3 , R5 and R 7 in L 1 of formula (2') are radicals other than hydrogen having the definitions and preferred meanings indicated above for R 5 .
- a likewise preferred use according to the invention of at least one metal complex compound of formula (1 ') as a catalyst for oxidation reactions is the use of such a compound wherein at least one of the substituents Ri to R 10 in L' of formula (2'), preferably R 3 , Rs and/or R 7 , is one of the following radicals: -(C 1 -C 6 alkylene)-N ⁇ R 13 R ⁇ 4 R 15 ; -N(R 12 )-(d-C 6 alkylene)-N ⁇ R 13 R 14 R 15 ; -N[(Ci-C 6 alkylene)-N e R 13 R 14 Ris] 2 ; -N(R 12 )-N ⁇ R 13 R 14 R 1S , wherein R 12 is as defined above and R 13l R ⁇ 4 and R i5 are each independently of the others hydrogen or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl, or R 3 and R 4
- R 13 and R ⁇ 4 together with the nitrogen atom linking them, form a 5-, 6- or 7-membered ring which is unsubstituted or substituted by at least one unsubstituted Ci-dalkyl and/or substituted C ⁇ -C alkyl and may contain further hetero atoms, wherein at least one nitrogen atom not bonded to one of three rings A, B and/or C is quaternised.
- a likewise more preferred use according to the invention of at least one metal complex compound of formula (1 ') as a catalyst for oxidation reactions is the use of such a compound wherein at least one of the substituents Ri to Rio in L', preferably R 3 , R 5 and or R 7 , is one of the following radicals: -(d-C 4 alkylene)-N ⁇ R 13 Ri4R ⁇ s; -N(R 12 )-(d-C 4 alkylene)-N ⁇ R 13 R ⁇ 4 Ri5; -N[(d-C 4 alkylene)-N ⁇ R 13 R 14 R 15 ] 2 ; -N(R 12 )-N ⁇ R 13 R 14 R 1S , wherein R 12 is hydrogen, unsubstituted or substituted d-C ⁇ 2 alkyl or unsubstituted or substituted aryl and R ⁇ 3 , R i and R 15 are each independently of the others hydrogen or unsubstituted or substituted d-C ⁇ 2
- a likewise important use according to the invention of at least one metal complex compound of formula (1 ') as a catalyst for oxidation reactions is the use of such a compound wherein at least one of the substituents Ri to Rio in L' of formula (2'), preferably R 3 , R 5 and/or R 7 , is a radical
- a likewise especially important use according to the invention of at least one metal complex compound of formula (1 ') as a catalyst for oxidation reactions is the use of such a compound wherein at least one of the substituents R T to R 1 0 in L' of formula (2'), preferably R 3 , R 5 and/or R 7 , is a radical
- unbranched or branched alkylene group may be unsubstituted or substituted and wherein the alkyl groups, each independently of the other, may be unsubstituted or substituted.
- the piperazine ring may also be unsubstituted or substituted.
- Ligands L' to which preference is given are those of formula (3'a) and/or (3'b)
- R' 3 , R' 5 and R' 7 have the definitions and preferred meanings indicated above for R 5 , but R' 3 and R' 7 may additionally be hydrogen.
- Ligands L' to which greater preference is given are those of formula (3'a) and/or (3'b) wherein R' 3 , R' 5 and R' 7 have the definitions and preferred meanings indicated above for R 5 , but R' 3 and R' 7 may additionally be hydrogen, with the proviso that (i) at least one of the substituents R' 3l R' 5 and R' 7 is a radical
- R i2 is as defined above and
- Ri3, R and R ⁇ S are each independently of the others. hydrogen or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl, or
- R 13 and R 4 together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms; or
- Ligands L' to which even greater preference is given are those of formula (3'a) and/or (3'b) wherein
- R' 3) R's and R' 7 have the definitions and preferred meanings indicated above for R 5 but R' 3 and R' 7 may additionally be hydrogen, with the proviso that
- Ligands L' to which special preference is given are those of formula (3'a) and/or (3'b) wherein
- R' 7 may additionally be hydrogen, with the proviso that
- unbranched or branched alkylene group may be unsubstituted or substituted, and wherein the alkyl groups, which are branched or unbranched independently of one another, may be unsubstituted or substituted and wherein the piperazine ring may be unsubstituted or substituted.
- L' are compounds of formulae (2'), (3'a) and (3'b) in which 1 quaternised nitrogen atom is present.
- L' compounds of formulae (2'), (3'a) and (3'b) in which 2 or 3 quaternised nitrogen atoms are present.
- L' compounds of formulae (2'), (3'a) and (3'b) in which none of the quaternised nitrogen atoms is bonded directly to one of three rings A, B and/or C.
- the metal complex compounds of formulae (1 ) and (1 ') can be obtained analogously to known processes. They are obtained in a manner known perse by reacting at least one ligand L and/or L' in the desired molar ratio with a metal compound, especially a metal salt, such as the chloride, to form the corresponding metal complex.
- a metal compound especially a metal salt, such as the chloride.
- the reaction is carried out, for example, in a solvent, such as water or a lower alcohol, such as ethanol, at a temperature of, for example, from 10 to 60°C, especially at room temperature.
- Ligands L and L' that are substituted by hydroxy can also be depicted in one or more tautomeric forms in accordance with the following scheme:
- the present invention relates also to novel metal complex compounds of formula (1 a) [L n Me m X p ] z Y q (1 a),
- Me is manganese, titanium, iron, cobalt, nickel or copper
- X is a coordinating or bridging radical
- n and m are each independently of the other an integer having a value of from 1 to 8
- p is an integer having a value of from 0 to 32
- z is the charge of the metal complex
- Y is a counter-ion
- q z/(charge of Y)
- L is a ligand of formula (2a)
- R 4> Rs, Re, R7, Re, g and R i0 are each independently of the others hydrogen; unsubstituted or substituted C ⁇ -C. 8 alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro; -COORn or -SO 3 Rn wherein
- Rn is in each case hydrogen, a cation or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl; -SR 12 , -SO 2 R i2 or -OR i2 wherein R 12 is in each case hydrogen or unsubstituted or substituted d-C 18 alkyl or unsubstituted or substituted aryl; -NR 1 3R 14 ; -(CrC 6 alkylene)-NR 13 R 14 ;
- R 12 is as defined above and
- Ri3, R ⁇ and R ⁇ 5 are each independently of the other(s) hydrogen or unsubstituted or substituted d-C 18 alkyl or unsubstituted or substituted aryl, or
- R 1 3 and R 1 together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms.
- Suitable substituents for the alkyl groups, aryl groups, alkylene groups or 5-, 6- or 7- membered rings are especially C 1 -C 4 alkyl; d-dalkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-d-C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino; phenyl; phenoxy or naphthyloxy.
- the d-C ⁇ 8 alkyl radicals mentioned for the compounds of formula (2a) are, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl.
- the mentioned alkyl radicals may be unsubstituted or substituted e.g.
- aryl radicals that come into consideration for the compounds of formula (2a) are phenyl or naphthyl each unsubstituted or substituted by C ⁇ -C 4 alkyl, d-C alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N- naphthylamino, wherein the amino groups may be quaternised, phenyl, phenoxy or by naphthyloxy.
- Preferred substituents are Ci-dalkyl, C ⁇ -C 4 alkoxy, phenyl and hydroxy. Special preference is given to the corresponding phenyl radicals.
- d-dalkylene groups mentioned for the compounds of formula (2a) are, for example, straight-chain or branched alkylene radicals, such as methylene, ethylene, n-propylene or n-butylene.
- d-C Alkylene groups are preferred.
- the alkylene radicals mentioned may be unsubstituted or substituted, for example by hydroxy or d-C 4 alkoxy.
- halogen is preferably chlorine, bromine or fluorine, with special preference being given to chlorine.
- Examples of cations that come into consideration for compounds of formulae (1a) and (2a) include alkali metal cations, such as lithium, potassium and especially sodium, alkaline earth metal cations, such as magnesium and calcium, and ammonium cations.
- alkali metal cations such as lithium, potassium and especially sodium
- alkaline earth metal cations such as magnesium and calcium
- ammonium cations are preferred.
- Suitable metal ions for Me for the compounds of formula (1a) are, for example, manganese in oxidation states ll-V, titanium in oxidation states III and IV, iron in oxidation states I to IV, cobalt in oxidation states I to III, nickel in oxidation states I to III and copper in oxidation states I to III, with special preference being given to manganese, especially manganese in oxidation states II to IV, preferably in oxidation state II. Also of interest are titanium IV, iron ll-IV, cobalt ll-lll, nickel ll-lll and copper ll-lll, especially iron ll-IV.
- radical X for the compounds of formula (1a) there come into consideration, for example, CH 3 CN, H 2 O, F “ , CI “ , Br “ , HOO “ , O 2 2” , O 2” , R 16 COO “ , R 16 O “ , LMeO ' and LMeOO ' , wherein R ⁇ 6 is hydrogen, -SO 3 d-C 4 alkyl or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl, and d-C 18 alkyl, aryl, L and Me have the definitions and preferred meanings given hereinabove and hereinbelow. Especially preferably, R ⁇ 6 is hydrogen; d-C 4 alkyl; sulfophenyl or phenyl, especially hydrogen.
- R 1 as d-C ⁇ 8 alkyl or aryl has the definitions and preferred meanings given hereinabove and hereinbelow.
- R ⁇ 7 is hydrogen; Ci-dalkyl; phenyl or sulfophenyl, especially hydrogen or 4-sulfophenyl.
- the charge of the counter-ion Y is accordingly preferably 1 - or 2-, especially 1 -.
- Y can also be a customary organic counter-ion, for example citrate, oxalate or tartrate.
- n is preferably an integer having a value of from 1 to 4, preferably 1 or 2 and especially 1.
- m is preferably an integer having a value of 1 or 2, especially 1.
- p is preferably an integer having a value of from 0 to 4, especially 2.
- z is preferably an integer having a value of from 8- to 8+, especially from 4- to 4+ and especially preferably from 0 to 4+. z is more especially the number 0.
- q is preferably an integer from 0 to 8, especially from 0 to 4, and is especially preferably the number 0.
- Rn in compounds of formula (2a) is preferably hydrogen, a cation, C ⁇ -C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- Rn is hydrogen, an alkali metal cation, alkaline earth metal cation or ammonium cation, Ci-dalkyl or phenyl, especially hydrogen or an alkali metal cation, alkaline earth metal cation or ammonium cation.
- Ri 2 in compounds of formula (2a) is preferably hydrogen, C ⁇ -C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- R ⁇ 2 is hydrogen, d-C 4 alkyl or phenyl, especially hydrogen or d-C alkyl, preferably hydrogen.
- Examples of the radical of formula -OR ⁇ 2 that may be mentioned are hydroxy and d-C 4 alkoxy, such as methoxy and especially ethoxy.
- R 1 3 and R 4 in compounds of formula (2a) together with the nitrogen atom linking them, form a 5-, 6- or 7-membered ring, that ring is preferably an unsubstituted or d-dalkyl- substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring, wherein the amino groups may be quaternised, in which case preferably the nitrogen atoms that are not bonded directly to one of the three rings A, B or C are quaternised.
- the piperazine ring may, for example, be substituted by one or two unsubstituted d-C alkyl and/or substituted d-C 4 alkyl at the nitrogen atom not bonded to the pyridine ring.
- R ⁇ 3 , R ⁇ 4 and R ⁇ 5 are preferably hydrogen, unsubstituted or hydroxy-substituted C ⁇ -C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- R 5 in L of formula (2a) is preferably d-C ⁇ 2 alkyl; phenyl unsubstituted or substituted by d-dalkyl, d-C alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N,N-di-d-C alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or by naphthyloxy; cyano; halogen; nitro; -COORn or -SO 3 Rn wherein R is in each case hydrogen, a cation, C C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above; -SR ⁇ 2 , -SO 2
- R 5 in L of formula (2a) is especially preferably phenyl unsubstituted or substituted by d-dalkyl, C r C 4 alkoxy, halogen, phenyl or by hydroxy; cyano; nitro; -COORn or -SO 3 Rn wherein Rn is in each case hydrogen, a cation, Ci-dalkyl or phenyl; -SR ⁇ 2 , -SO 2 R 12 or -OR 12 wherein R 12 is in each case hydrogen, d-C 4 alkyl or phenyl; -N(CH 3 )-NH 2 or -NH-NH 2 ; amino; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or an unsubstituted or d-C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or a
- R 5 in L of formula (2a) is very especially preferably d-C 4 alkoxy; hydroxy; phenyl unsubstituted or substituted by d-C 4 alkyl, C r C alkoxy, phenyl or by hydroxy; hydrazine; amino; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or an unsubstituted or d-C 4 alkyl-s ⁇ bstituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- radicals R 5 in L of formula (2a) there are especially important d-C 4 alkoxy; hydroxy; hydrazine; amino; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or an unsubstituted or d-C alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- radicals R 5 in L of formula (2a) there are very especially important d-C alkoxy; hydroxy; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; and an unsubstituted or d-dalkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- hydroxy is of special interest.
- the preferred meanings given above for R s apply also to Ri, R 2 , R 3 , R 4 , R 6 , R7, Rs, Rg and R10 in L of formula (2a), but those radicals may additionally be hydrogen.
- Ri, R 2 , R 3 , R 4 , Re, R7, Re, Rg and R 0 in L of formula (2a) are hydrogen and R 5 in L of formula (2a) is a radical other than hydrogen having the definition and preferred meanings indicated above.
- Ri, R 2 , R 4 , R 6 , R 8 , Rg and R 10 in L of formula (2a) are hydrogen and R 3 , R 5 and R in L of formula (2a) are radicals other than hydrogen, for each of which the definition and preferred meanings indicated above for R 5 apply.
- Ligands L to which preference is given are those of formula (3a) and/or (3b)
- R' 3 and R' s have the definitions and preferred meanings indicated above for R 3 and R 5
- R' 7 has the definition and preferred meanings indicated above for R s .
- Metal complexes to which greater preference is given especially manganese(ll) and/or iron(ll) complexes, of formula (1a), contain as ligands L those of formula (3a) and/or (3b)
- R' 3 , R' 5 and R' 7 have the definitions and preferred meanings indicated above for R 5 , but R' 3 and R' 7 may additionally be hydrogen.
- Especially preferred metal complexes especially manganese(ll) and/or iron (II) complexes, of formula (1 a), contain as ligands L those of formula (3a) and/or (3b)
- R's is C ⁇ -C 4 alkoxy; hydroxy; N-mono- or N,N-di-d-C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or -NR ⁇ 3 R ⁇ 4 ; -(d-C 6 alkylene)-NR 3 R ⁇ 4 ;
- R 12 is hydrogen; d-d 2 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-C ⁇ -C 4 alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and
- R13 and R ⁇ are each independently of the other hydrogen, unsubstituted or hydroxy-substituted d-C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or
- R 1 3 and R ⁇ together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted d-dalkyl and/or substituted Ci- dalkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring, and R' 3 and R' 7 are each independently of the other hydrogen; d-C 4 alkoxy; hydroxy; N-mono- or N,N-di-C ⁇ -C alkylamino substituted by hydroxy in the alkyl moiety; or -NRi 3 R 14 ; -(C ⁇ -Cealkylene)-NR ⁇ 3 R ⁇ 4 ; -N(R ⁇ 2 )-(C ⁇ -C 6 alkylene)-NR ⁇ 3 R ⁇ 4 ; -N[(d-C 6 alkylene)-NR ⁇ 3
- R ⁇ 2 is hydrogen; C ⁇ -C ⁇ 2 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-C ⁇ -C alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and
- R ⁇ 3 and R are each independently of the other hydrogen; unsubstituted or hydroxy-substituted d-C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or
- R ⁇ 3 and R ⁇ 4 together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted Ci-dalkyl and/or substituted d-C 4 alkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- the present invention relates also to novel metal complex compounds of formula (1 'a)
- Me is manganese, titanium, iron, cobalt, nickel or copper
- X is a coordinating or bridging radical
- n and m are each independently of the other an integer having a value of from 1 to 8
- p is an integer having a value of from 0 to 32
- z is the charge of the metal complex
- Y is a counter-ion
- q z (charge of Y)
- L' is a ligand of formula (2'a) wherein
- Ri, R2, R3, R 4 , Rs, Re, R7, Re, Rg and R 0 are each independently of the others hydrogen; unsubstituted or substituted C C ⁇ 8 alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro; -COORn or -SO 3 R ⁇ wherein
- R 11 is in each case hydrogen, a cation or unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl; -SR i2 , -SO 2 R ⁇ 2 or -OR ⁇ 2 wherein
- R ⁇ 2 is in each case hydrogen or unsubstituted or substituted Ci-Cisalkyl or substituted or unsubstituted aryl; -NR ⁇ 3 R ⁇ 4 ; -(C C 6 alkylene)-NR ⁇ 3 R 14 ; -N ⁇ R ⁇ 3 R ⁇ 4 R ⁇ S ;
- R ⁇ 2 is as defined above and
- Ri3, R ⁇ and R 1 5 are each independently of the other(s) hydrogen or unsubstituted or substituted C ⁇ -C 8 alkyl or substituted or unsubstituted aryl, or
- R 1 3 and R ⁇ 4 together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms, with the proviso that, at least one of the substituents Ri to R i0 contains a quaternised nitrogen atom that is not bonded directly to one of the three rings A, B and/or C.
- Suitable substituents for the alkyl groups, aryl groups, alkylene groups or 5-, 6- or 7- membered rings are especially d-C 4 alkyl; d-C 4 alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-d-C alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino; phenyl; phenoxy or naphthyloxy.
- the C ⁇ -C ⁇ 8 alkyl radicals mentioned for the compounds of formula (2'a) are, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl.
- the mentioned alkyl radicals may be unsubstituted or substituted e.g.
- aryl radicals that come into consideration for the compounds of formula (2'a) are phenyl or naphthyl each unsubstituted or substituted by d-C 4 alkyl, d-dalkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N,N-di-C ⁇ -dalkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N- naphthylamino, wherein the amino groups may be quaternised, phenyl, phenoxy or by naphthyloxy.
- Preferred substituents are Ci-dalkyl, d-C 4 alkoxy, phenyl and hydroxy. Special preference is given to the corresponding phenyl radicals.
- the d-C 6 alkylene groups mentioned for the compounds of formula (2'a) are, for example, straight-chain or branched alkylene radicals, such as methylene, ethylene, n-propylene or n-butylene. d-dAlkylene groups are preferred.
- the alkylene radicals mentioned may be unsubstituted or substituted, for example by hydroxy or d-dalkoxy.
- halogen is preferably chlorine, bromine or fluorine, with special preference being given to chlorine.
- Examples of cations that come into consideration for compounds of formulae (1'a) and (2'a) include alkali metal cations, such as lithium, potassium and especially sodium, alkaline earth metal cations, such as magnesium and calcium, and ammonium cations.
- alkali metal cations, especially sodium are preferred.
- Suitable metal ions for Me for the compounds of formula (1'a) are, for example, manganese in oxidation states ll-V, titanium in oxidation states III and IV, iron in oxidation states I to IV, cobalt in oxidation states I to III, nickel in oxidation states I to III and copper in oxidation states I to III, with special preference being given to manganese, especially manganese in oxidation states II to IV, preferably in oxidation state II. Also of interest are titanium IV, iron ll-IV, cobalt ll-lll, nickel ll-lll and copper ll-lll, especially iron ll-IV.
- radical X for the compounds of formula (1 'a) there come into consideration, for example, CH 3 CN, H 2 O, F, CI “ , Br “ , HOO ' , O 2 2' , O 2' , R ⁇ 6 COO ' , R ⁇ 8 O “ , LMeO " and LMeOO " , wherein R ⁇ 6 is hydrogen, -SO 3 C C 4 alkyl or unsubstituted or substituted d-C ⁇ 8 alkyl or substituted or unsubstituted aryl, and d-C ⁇ 8 alkyl, aryl, L and Me have the definitions and preferred meanings given hereinabove and hereinbelow. Especially preferably, R ⁇ 6 is hydrogen; Ci-dalkyl; sulfophenyl or phenyl, especially hydrogen.
- R ⁇ 7 is hydrogen; Ci-dalkyl; phenyl or sulfophenyl, especially hydrogen or 4-sulfophenyl.
- the charge of the counter-ion Y is accordingly preferably 1- or 2-, especially 1-.
- Y can also be a customary organic counter-ion, for example citrate, oxalate or tartrate.
- n is preferably an integer having a value of from 1 to 4, preferably 1 or 2 and especially 1.
- m is preferably an integer having a value of 1 or 2, especially 1.
- p is preferably an integer having a value of from 0 to 4, especially 2.
- z is preferably an integer having a value of from 8- to 8+, especially from 4- to 4+ and especially preferably from 0 to 4+. z is more especially the number 0.
- Rn in compounds of formula (2'a) is preferably hydrogen, a cation, C ⁇ -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- R is hydrogen, an alkali metal cation, alkaline earth metal cation or ammonium cation, d-C alkyl or phenyl, especially hydrogen or an alkali metal cation, alkaline earth metal cation or ammonium cation.
- R ⁇ 2 in compounds of formula (2'a) is preferably hydrogen, d-C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- R i2 is hydrogen, Ci-dalkyl or phenyl, especially hydrogen or C ⁇ -C 4 alkyl, preferably hydrogen.
- Examples of the radical of formula -OR ⁇ 2 that may be mentioned are hydroxy and d-dalkoxy, such as methoxy and especially ethoxy.
- R ⁇ 3 and R 14 in compounds of formula (2'a) together with the nitrogen atom linking them, form a 5-, 6- or 7-membered ring, that ring is preferably an unsubstituted or C ⁇ -C 4 alkyl- substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring, wherein the amino groups may be quaternised, in which case preferably the nitrogen atoms that are not bonded directly to one of the three rings A, B or C are quaternised.
- the piperazine ring may, for example, be substituted by one or two unsubstituted d-dalkyl and/or substituted C ⁇ -C alkyl at the nitrogen atom not bonded to the pyridine ring.
- R ⁇ 3 , R and R ⁇ 5 are preferably hydrogen, unsubstituted or hydroxy-substituted C ⁇ -C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- R' 3 and RV may additionally be hydrogen.
- Ligands L' to which greater preference is given are those of formula (3'a) and/or (3'b) wherein R' 3 , R' s and R' 7 have the definitions and preferred meanings indicated above for R 5 , but R' 3 and R' 7 may additionally be hydrogen, with the proviso that
- R 12 is as defined above and
- R13, R ⁇ 4 and R ⁇ 5 are each independently of the others hydrogen or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl, or
- Ri 3 and R ⁇ together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms; or
- 7-membered ring which may be unsubstituted or substituted by at least one unsubstituted d-C 4 alkyl and/or substituted Ci-dalkyl and may contain further hetero atoms, wherein at least one nitrogen atom not bonded to one of the rings A, B and7or
- Ligands L' to which even greater preference is given are those of formula (3'a) and/or (3'b) wherein R' 3) R' s and R' 7 have the definitions and preferred meanings indicated above for R 5 but R' 3 and R' 7 may additionally be hydrogen, with the proviso that (i) at least one of the substituents R' 3l R' s and R' 7 is one of the radicals
- unbranched or branched alkylene group may be unsubstituted or substituted, and wherein the alkyl groups, which are branched or unbranched independently of one another, may be unsubstituted or substituted and wherein the piperazine ring may be unsubstituted or substituted.
- Ligands L' to which special preference is given are those of formula (3'a) and/or (3'b) wherein R' 3 , R' s and R' 7 have the definitions and preferred meanings given above for R 5 , but R' 3 and R' 7 may additionally be hydrogen, with the proviso that (i) at least one of the substituents R' 3 , R' 5 and R' 7 is one of the radicals
- unbranched or branched alkylene group may be unsubstituted or substituted, and wherein the alkyl groups, which are branched or unbranched independently of one another, may be unsubstituted or substituted and wherein the piperazine ring may be unsubstituted or substituted.
- L' are compounds of formulae (2'), (3'a) and (3'b) in which 1 quaternised nitrogen atom is present.
- L' compounds of formulae (2'), (3'a) and (3'b) in which 2 or 3 quaternised nitrogen atoms are present.
- L' Especially preferred as L' are compounds of formulae (2'), (3'a) and (3'b) in which none of the quaternised nitrogen atoms is bonded directly to one of the rings A, B or C.
- the present invention relates also to the novel ligands L' of formulae (4') and (5')
- Ri, R2, R3, R , Rs, Re, R7, Re, Rg and R10 are each independently of the others hydrogen; unsubstituted or substituted Ci-Ciaalkyl or unsubstituted or substituted aryl; cyano; halogen; nitro; -COORn or -SO 3 Rn wherein
- R 11 is in each case hydrogen, a cation or unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl; -SR ⁇ 2 , -SO 2 R ⁇ 2 or -OR ⁇ 2 wherein R ⁇ 2 is in each case hydrogen or unsubstituted or substituted CrC 8 alkyl or unsubstituted or substituted aryl; -NR ⁇ 3 R ⁇ 4 ; -(C ⁇ -C 6 alkylene)-NR ⁇ 3 R ⁇ ; -N ⁇ R ⁇ 3 R ⁇ 4 R 1s ;
- R ⁇ 2 is as defined above and
- R 1 3, R ⁇ 4 and R ⁇ 5 are each independently of the other(s) hydrogen or unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl, or
- R ⁇ 3 and R ⁇ 4 together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms, with the proviso that at least one of the substituents Ri to Rio contains a quaternised nitrogen atom that is not bonded directly to one of the three rings A, B and/or C.
- Suitable substituents for the alkyl groups, aryl groups, alkylene groups or 5-, 6- or 7- membered rings are especially Ci-dalkyl; d-C alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino; phenyl; phenoxy or naphthyloxy.
- the C ⁇ -C ⁇ 8 alkyl radicals mentioned for the compounds of formulae (4') and (5') are, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl.
- the mentioned alkyl radicals may be unsubstituted or substituted e.g.
- aryl radicals that come into consideration for the compounds of formulae (4') and (5') are phenyl or naphthyl each unsubstituted or substituted by C ⁇ -C 4 alkyl, C ⁇ -C 4 alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N,N-di-CrC 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthyl- amino, wherein the amino groups may be quaternised, phenyl, phenoxy or by naphthyloxy.
- Preferred substituents are d-C 4 alkyl, d-C 4 alkoxy, phenyl and hydroxy. Special preference is given to the corresponding phenyl radicals.
- the C ⁇ -C 6 alkylene groups mentioned for the compounds of formulae (4') and (5') are, for example, straight-chain or branched alkylene radicals, such as methylene, ethylene, n-propylene or n-butylene. C ⁇ -C 4 Alkylene groups are preferred.
- the alkylene radicals mentioned may be unsubstituted or substituted, for example by hydroxy or d-dalkoxy.
- Examples of cations that come into consideration for compounds of formulae (4') and (5') include alkali metal cations, such as lithium, potassium and especially sodium, alkaline earth metal cations, such as magnesium and calcium, and ammonium cations.
- alkali metal cations such as lithium, potassium and especially sodium
- alkaline earth metal cations such as magnesium and calcium
- ammonium cations are preferred.
- halogen is preferably chlorine, bromine or fluorine, with special preference being given to chlorine.
- Rn in compounds of formulae (4') and (5') is preferably hydrogen, a cation, d-C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- Rn is hydrogen, an alkali metal cation, alkaline earth metal cation or ammonium cation, Ci-dalkyl or phenyl, especially hydrogen or an alkali metal cation, alkaline earth metal cation or ammonium cation.
- R12 in compounds of formulae (4') and (5') is preferably hydrogen, d-C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- R ⁇ 2 is hydrogen, d-dalkyl or phenyl, especially hydrogen or d-C alkyl, preferably hydrogen.
- Examples of the radical of formula -OR12 that may be mentioned are hydroxy and d-C 4 alkoxy, such as methoxy and especially ethoxy.
- the piperazine ring may, for example, be substituted by one or two unsubstituted C ⁇ -C 4 alkyl and/or substituted d-C 4 alkyl at the nitrogen atom not bonded to the pyridine ring.
- R 13 , R and R ⁇ s are preferably hydrogen, unsubstituted or hydroxy-substituted C ⁇ -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above.
- Special preference is given to hydrogen, unsubstituted or hydroxy-substituted d-dalkyl, or phenyl, especially hydrogen or unsubstituted or hydroxy-substituted d-C 4 alkyl, preferably hydrogen.
- Preference is given to compounds of formulae (4') and (5') wherein R 5 is not hydrogen.
- R 5 is preferably phenyl unsubstituted or substituted by C ⁇ -C 4 alkyl, d-C 4 alkoxy, halogen, phenyl or by hydroxy; cyano; nitro; -COORn or -SO 3 Rn wherein Rn is in each case hydrogen, a cation, d-C 4 alkyl or phenyl; -SR ⁇ 2 , -SO 2 R 12 or -OR ⁇ 2 wherein R 2 is in each case hydrogen, C ⁇ -C 4 alkyl or phenyl; -N(CH 3 )-NH 2 or -NH-NH ; amino; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety wherein the nitrogen atoms, especially the nitrogen atoms not bonded to one of the three rings A, B or C, may be
- R 5 in compounds of formulae (4') and (5') is very especially d-C 4 alkoxy; hydroxy; phenyl unsubstituted or substituted by d-C alkyl, C ⁇ -C 4 alkoxy, phenyl or by hydroxy; hydrazine; amino; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms not bonded to one of the three rings A, B or C, may be quaternised; or a pyrrolidine, piperidine, morpholine or azepane ring unsubstituted or substituted by one or two unsubstituted Ci-dalkyl and/or substituted C ⁇ -C 4 alkyl, wherein the nitrogen atom may be quaternised.
- a likewise very especially preferred radical that may be mentioned for R 5 in compounds of formulae (4') and (5') is wherein the ring, the alkylene group and the two alkyl groups may additionally be substituted.
- radicals R 5 in compounds of formulae (4 1 ) and (5') there are especially important d-C 4 alkoxy; hydroxy; hydrazine; amino; N-mono- or N,N-di-C ⁇ -C alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms not bonded to one of the three rings A, B or C, may be quaternised; or a pyrrolidine, piperidine, piperazine, morpholine or azepane ring unsubstituted or substituted by at least one d-dalkyl, wherein the nitrogen atoms may be quaternised.
- ring, the alkylene group and the two alkyl groups may additionally independently from each other substituted.
- radicals R 5 in compounds of formulae (4') and (5') there are especially important d-C 4 alkoxy; hydroxy; N-mono- or N,N-di-C ⁇ -C 4 alkylamino substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms not bonded to one of the three rings A, B or C, may be quaternised; or a pyrrolidine, piperidine, morpholine or azepane ring unsubstituted or substituted by at least one d-C 4 alkyl, wherein the amino groups may be quaternised.
- radical R 5 in compounds of formulae (4') and (5') mention may be made especially of -OH; ,CH 2 CH 2 OH / + ⁇ CH 2 CH 2 OH _. . +,
- hydroxy is of special interest.
- R 5 in L' of formula (2') applies also to R 1( R 2 , R 3 , R 4 , Re, R7, Re, Rg and R10 in compounds of formulae (4') and (5'), but those radicals may additionally be hydrogen.
- Ri, R 2> R 3 , R 4 , R 6 , R 7 , R 8 , Rg and R 10 in compounds of formulae (4') and (5') are hydrogen and R 5 in L' of formula (2') is a radical other than hydrogen having the definition and preferred meanings indicated above.
- R 1 t R 2 , R 4 , R 6 , R 8 , Rg and R10 in compounds of formulae (4') and (5') are hydrogen and R 3 , R 5 and R 7 in compounds of formulae (4') and (5') are radicals other than hydrogen, for each of which the definitions and preferred meanings indicated above for R s apply.
- unbranched or branched alkylene group may be unsubstituted or substituted and wherein the alkyl groups, which are unbranched or branched independently of one another, may be unsubstituted or substituted.
- the piperazine ring may also be unsubstituted or substituted.
- R' 3 , R' 5 and R' 7 have the definitions and preferred meanings given above for R 5 in compounds of formulae (4') and (5'), but R' 3 and R' 7 may additionally be hydrogen.
- R' 3 and R' 7 may additionally be hydrogen, with the proviso that
- R 2 is as defined above and
- R ⁇ 3 , Ri 4 and R 15 are each independently of the others hydrogen or unsubstituted or substituted d-C 18 alkyl or unsubstituted or substituted aryl, or
- R ⁇ 3 and R ⁇ 4 together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms; or
- R i2 is as defined above and R13 and R , together with the nitrogen atom linking them, form a 5-, 6- or 7-membered ring which may be unsubstituted or substituted by at least one unsubstituted Ci-dalkyl and/or substituted Ci-dalkyl and may contain further hetero atoms, wherein at least one nitrogen atom not bonded to one of the rings A, B and/or C is quaternised.
- R' 3 and R' 7 may additionally be hydrogen, with the proviso that
- V,-o 4 .-alkyl " an * ⁇ ro * r wherein the unbranched or branched alkylene group may be unsubstituted or substituted, and wherein the alkyl groups, which are branched or unbranched independently of one another, may be unsubstituted or substituted and wherein the piperazine ring may be unsubstituted or substituted.
- R' 3 and R' 7 may additionally be hydrogen, with the proviso that
- R' 3 is one of the radicals
- unbranched or branched alkylene group may be unsubstituted or substituted, and wherein the alkyl groups, which are branched or unbranched independently of one another, may be unsubstituted or substituted and wherein the piperazine ring may be unsubstituted or substituted.
- Ri, R2, R4, Rs, R$, R 7 , Re and R 9 are each independently of the others hydrogen; unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro; -COORn or -SO Rn wherein
- R 11 is in each case hydrogen, a cation or unsubstituted or substituted C ⁇ -C 18 alkyl or substituted or unsubstituted aryl; -SR 12 , -SO 2 R 1 2 or -OR ⁇ 2 wherein
- R ⁇ 2 is in each case hydrogen or unsubstituted or substituted d-C 8 alkyl or unsubstituted or substituted aryl; -NR13R 14 ; -(C ⁇ -C 6 alkylene)-NR 13 R ⁇ 4 ; -N ⁇ R 13 R ⁇ 4 R ⁇ 5 ;
- R ⁇ 2 is as defined above and
- Ri 3 , R ,4 and R15 are each independently of the other(s) hydrogen or unsubstituted or substituted C ⁇ -C 8 alkyl or unsubstituted or substituted aryl, or
- R ⁇ 3 and R together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms, and
- R 3 is phenyl substituted by d-C 4 alkyl, d-C 4 alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono- or N,N-di-C ⁇ -C alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or by naphthyloxy, substituted d-C ⁇ 8 alkyl or substituted or unsubstituted aryl; -CH 3 ; C 3 -d 8 alkyl; cyano; halogen; nitro; -COORn or -SO 3 Rn wherein
- Rn is in each case hydrogen, a cation or unsubstituted or substituted d-C ⁇ 8 alkyl or substituted or unsubstituted aryl; -SR i2 , -SO 2 R ⁇ 2 or -OR ⁇ 2 wherein R ⁇ 2 is in each case hydrogen or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl; -NR ⁇ 3 R ⁇ 4 ; -(d-C 6 alkylene)-NR ⁇ 3 R ⁇ 4 ; -N ⁇ R ⁇ 3 R 14 R ⁇ 5 ;
- R ⁇ 2 is as defined above and
- R 13 , R ⁇ 4 and R ⁇ 5 are each independently of the other(s) hydrogen or unsubstituted or substituted C ⁇ -C 18 alkyl or substituted or unsubstituted aryl, or
- R 1 3 and R together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms.
- R' 3 and R' 7 have the definitions and preferred meanings indicated above for R 3 and R 7
- R' 5 has the definition and preferred meanings indicated above for R 5 .
- R's is d-dalkoxy; hydroxy; N-mono- or N,N-di-C ⁇ -C 4 alkylamino substituted by hydroxy in the alkyl moiety; or -NR ⁇ 3 R ⁇ 4 ; -(C ⁇ -C 6 alkylene)-NR ⁇ 3 R ⁇ 4 ; -N(R ⁇ 2 )-(C ⁇ -Cealkylene)-NRi 3 R ⁇ ; -N[(C ⁇ -Cealkylene)-NRi 3 Ri 4 ] 2 ; or -N(R ⁇ 2 )-N-R ⁇ 3 R, 4 , wherein
- R 2 is hydrogen; C C 12 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-C ⁇ -C alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy,
- R ⁇ 3 and R i4 are each independently of the other hydrogen; unsubstituted or hydroxy-substituted C ⁇ -C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above or R ⁇ 3 and R 14 , together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted d-C alkyl and/or substituted Ci- dalkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring, and R' 3 is C ⁇ -C 4 alkoxy; hydroxy; N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or -NR 3 R 14 ; -(d-C 6 al
- R 12 is hydrogen; C ⁇ -C ⁇ 2 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-d-C 4 alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and
- R ⁇ 3 and R 4 are each independently of the other hydrogen; unsubstituted or hydroxy-substituted CrC ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or
- R ⁇ 3 and R ⁇ 4 together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted d-dalkyl and/or substituted d-dalkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring, and R' 7 is hydrogen; d-dalkoxy; hydroxy; N-mono- or N,N-di-C ⁇ -C 4 alkylamino substituted by hydroxy in the alkyl moiety; or -NR 13 R 1 ; -(C ⁇ -C 6 alkylene)-NR 13 R 4 ; -N(R ⁇ 2 )-(C ⁇ -C 6 alkylene)-NR ⁇ 3 R ⁇ 4 ; -N[(C r C 6 alkylene)-NR ⁇ 3 R ⁇ 4 ] 2 ; or
- Ri 2 is hydrogen; d-C 2 alkyl or unsubstituted or (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-C ⁇ -C alkylamino-, N-phenylamino-,
- R 1 3 and R ⁇ 4 are each independently of the other hydrogen; unsubstituted or hydroxy-substituted CrC ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or
- Ri 3 and R ⁇ 4 together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted d-C 4 alkyl and/or substituted d-C 4 alkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- the present invention relates also to the novel ligands L of formula (7)
- R-i, R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 and R i0 are each independently of the others hydrogen; unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro; -COORn or -SO 3 Rn wherein
- Rn is in each case hydrogen, a cation or unsubstituted or substituted C ⁇ -C 8 alkyl or substituted or unsubstituted aryl; -SR ⁇ 2 , -SO 2 R ⁇ 2 or -OR ⁇ 2 wherein
- R 12 is in each case hydrogen or unsubstituted or substituted d-C ⁇ 8 alkyl or substituted or unsubstituted aryl; -NR ⁇ 3 R ⁇ 4 ; -(C C 6 alkylene)-NR ⁇ 3 R ⁇ 4 ; -N ⁇ R ⁇ 3 R ⁇ 4 R ⁇ 5 ;
- R 12 is as defined above and
- Ri3, R ⁇ 4 and R ⁇ 5 are each independently of the other(s) hydrogen or unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl, or
- Ri 3 and R ⁇ 4 together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms, and
- R 7 is phenyl substituted by Ci-dalkyl, d-dalkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, amino, N-mono- or N,N-di-C ⁇ -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or by naphthyloxy, substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl; -CH 3 ; C 3 -d 8 alkyl; cyano; F; Br; I; nitro; -COORn or -SO 3 Rn wherein
- Rn is in each case hydrogen, a cation or unsubstituted or substituted d-C ⁇ 8 alkyl or unsubstituted or substituted aryl; -SR ⁇ 2 , -SO 2 R ⁇ 2 or -OR ⁇ 2 wherein
- R 12 is in each case hydrogen or unsubstituted or substituted C ⁇ -C ⁇ 8 alkyl or unsubstituted or substituted aryl; -NR ⁇ 3 R ; -(d-Cealkylene)-NR 13 Ri4; -N ⁇ R ⁇ 3 R 14 R ⁇ S ; -(d-C 6 alkylene)-N ⁇ R 13 R ⁇ 4 Ri 5 ; -N(R ⁇ 2 )-(C ⁇ -C 6 alkylene)-NR ⁇ 3 R ⁇ 4 ;
- R i2 is as defined above and
- R ⁇ 3 , R ⁇ 4 and Ris are each independently of the other(s) hydrogen or unsubstituted or substituted C ⁇ -C 18 alkyl or substituted or unsubstituted aryl, or
- R 1 3 and R together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms.
- R' 3 and R' 7 have the definitions and preferred meanings indicated above for R 3 and R 7
- R' 5 has the definition and preferred meanings indicated above for R 5 .
- R's is d-dalkoxy; hydroxy; N-mono- or N,N-di-C ⁇ -C 4 alkylamino substituted by hydroxy in the alkyl moiety; or - R ⁇ 3 R ⁇ 4 ; -(C ⁇ -C 6 alkylene)-NR ⁇ 3 R ⁇ 4 ;
- R ⁇ 2 is hydrogen; d-C ⁇ 2 alkyl or unsubstituted phenyl or phenyl substituted by
- R 1 3 and R M are each independently of the other hydrogen; unsubstituted or hydroxy-substituted d-C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or
- R 1 3 and R 14 together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted d-dalkyl and/or substituted Ci- dalkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring, and R' 3 is C ⁇ -C 4 alkoxy; hydroxy; N-mono- or N.N-di-d-dalkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or -NR 13 R ⁇ ; -(C ⁇ -C 6 alkylene)-NR ⁇ 3 R ⁇ 4 ;
- R ⁇ 2 is hydrogen; d-d 2 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-CrC 4 alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and
- R i3 and R 1 are each independently of the other hydrogen; unsubstituted or hydroxy-substituted d-C ⁇ alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or
- R 13 and R ⁇ 4 together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted d-dalkyl and/or substituted Ci- dalkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring, R' 7 is hydrogen, d-C 4 alkoxy; hydroxy; N-mono- or N,N-di-C ⁇ -C 4 alkylamino substituted by hydroxy in the alkyl moiety; or -NR 13 Ru; -(C ⁇ -C 6 alkylene)-NR ⁇ 3 Ri4',
- R- I2 is hydrogen; C C 12 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-C ⁇ -C 4 alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and
- R ⁇ 3 and R 1 are each independently of the other hydrogen; unsubstituted or hydroxy-substituted d-C ⁇ 2 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or
- R ⁇ 3 and R 14 together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted d-C 4 alkyl and/or substituted Ci- dalkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
- the metal complex compounds of formula (1 ) and/or (1 ') are used together with peroxy compounds.
- Examples that may be mentioned in that regard include the following uses: a) the bleaching of stains or soiling on textile material in the context of a washing process; b) the prevention of redeposition of migrating dyes during the washing of textile material; c) the cleaning of hard surfaces, especially kitchen surfaces, wall tiles or floor tiles, for example to remove stains that have formed as a result of the action of moulds ("mould stains") ; d) use in washing and cleaning solutions having an antibacterial action; e) as pretreatment agents for bleaching textiles; f) as catalysts in selective oxidation reactions in the context of organic synthesis, g) as catalysts for waste water treatment.
- a further use is concerned with the use of at least one metal complex compound of formula (1) and/or (V) as a catalyst for reactions with peroxy compounds for bleaching in the context of paper-making.
- This relates especially to the delignification of cellulose and bleaching of the pulp, which can be carried out in accordance with customary procedures.
- at least one metal complex compound of formula (1 ) and/or (1 ') as a catalyst for reactions with peroxy compounds for the bleaching of waste printed paper.
- the preferred metals are in this case manganese and/or iron.
- the metal complex compounds do not cause any appreciable damage to fibres and dyeings.
- the metal complexes are also used as catalysts for oxidation reactions using molecular oxygen and/or air.
- Processes for preventing the redeposition of migrating dyes in a washing liquor are usually carried out by adding to the washing liquor (which comprises a peroxide-containing detergent) from 0.1 to 200 mg, especially from 1 to 75 mg, more especially from 3 to 50 mg, of one or more metal complex compounds of formula (1) and/or (1 ') per litre of washing liquor.
- the washing liquor which comprises a peroxide-containing detergent
- a detergent that already comprises one or two metal complex compounds.
- the metal complex compounds of formula (1) and/or (1') can alternatively be formed in situ, the metal salt (e.g. manganese(ll) salt, such as manganese(ll) chloride, and/or iron(ll) salt, such as iron(ll) chloride) and the ligand being added in the desired molar ratios.
- the present invention furthermore relates to a combined process for the prevention of redeposition of migrating dyes and the simultaneous bleaching of stains or soiling on textile material.
- Metal complexes of formula (1) and or (1') especially manganese complexes of formula (1) and/or (1'), are used for that purpose. It is also possible to use manganese complexes of formula (1) and/or (1 ') together with iron complexes of formula (1) and/or (1').
- Processes for the prevention of redeposition of migrating dyes in a washing liquor are usually carried out by adding to the washing liquor (which comprises a peroxide-containing detergent) from 0.1 to 200 mg, especially from 1 to 75 mg, more especially from 3 to 50 mg, per litre of washing liquor, of manganese complexes of formula (1 ) and/or (1 '), optionally together with iron complexes of formula (1 ) and/or (1 ').
- the washing liquor which comprises a peroxide-containing detergent
- the washing liquor which comprises a peroxide-containing detergent
- the washing liquor which comprises a peroxide-containing detergent
- the washing liquor which comprises a peroxide-containing detergent
- the metal complex compounds of formula (1) and/or (V) can alternatively be formed in situ, the metal salt (e.g. manganese(ll) salt, such as manganese(ll) chloride, and/or iron(ll) salt, such as iron(ll) chloride) and the ligand being added in the desired molar ratios
- the present invention relates also to mixtures of manganese complexes of formula (1 ) and/or (1 ') with iron complexes of formula (1 ) and/or (1 ').
- the present invention relates also to a detergent, cleaning, disinfecting or bleaching composition containing
- the present invention relates also to a detergent, cleaning, disinfecting or bleaching composition that is free of peroxide and/or "peroxide-forming substance" and contains
- compositions preferably contain from 0.005 to 2% of a metal complex compound of formula (1 ), especially from 0.01 to 1% and preferably from 0.05 to 1 %.
- the amount thereof is preferably from 1 to 50%, especially from 1 to 30%.
- compositions according to the invention comprise a component C
- the amount thereof is preferably from 1 to 70%, especially from 1 to 50%. Special preference is given to an amount of from 5 to 50% by weight and especially an amount of from 10 to 50%.
- Corresponding detergent, cleaning, disinfecting or bleaching processes are usually carried out by using an aqueous liquor comprising a peroxide and from 0.1 to 200 mg of one or more compounds of formula (1 ) and/or (1 ') per litre of liquor.
- the liquor contains from 1 to 30 mg of at least one compound of formula (1 ) and/or (1 ') per litre of liquor.
- the composition according to the invention can be, for example, a peroxide-containing heavy-duty detergent or a separate bleaching additive.
- a bleaching additive is used in the removal of coloured stains on textiles in a separate liquor, before the clothes are washed with a bleach-free detergent.
- a bleaching additive can also be used in a liquor together with a bleach-free 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.
- Granules can be prepared, for example, by first preparing an initial powder by spray-drying an aqueous suspension comprising all the components listed above except for components D) and E, and then adding the dry components D) and E) and mixing everything together. It is also possible to add component E) to an aqueous suspension containing components A), B) and C), then carry out spray-drying, and then mix component D) with the dry mass.
- aqueous suspension that comprises components A) and C), but none or only some of component B).
- the suspension is spray-dried, then component E) is mixed with component B) and added, and finally component D) is admixed in the dry state.
- 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 ⁇ -sulfo ⁇ ic 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 radical, 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.
- Preferred carboxylates are alkali metal sarcosinates of formula R ⁇ 9 -CON(R 2 o)CH 2 COOM ⁇ wherein R ⁇ 9 is C 9 -C ⁇ 7 alkyl or C 9 -d 7 alkenyl, R 20 is d-C alkyl and i is an alkali metal, especially sodium.
- the non-ionic surfactant B) may be, for example, a primary or secondary alcohol ethoxylate, especially a C 8 -C 20 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 C ⁇ 0 -C ⁇ S 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 5 to 50% by weight, especially from 5 to 40% by weight and more especially from 5 to 30% by weight.
- the lower limit of those surfactants to which even greater preference is given is 10% by weight.
- 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 compounds.
- Silicates that are especially suitable are sodium salts of crystalline layered silicates of the formula NaHSi,O 2t+ ⁇ .pH 2 O or Na 2 Si t ⁇ 2t+ ⁇ .pH 2 O wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.
- zeolite A preference is given to those commercially available under the names zeolite A, B, X and HS, and also to mixtures comprising two or more such components. Special preference is given to zeolite A.
- 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.
- Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1 ,1 -diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta- methylenephosphonic acid, and also salts thereof.
- Suitable peroxides include, for example, organic and inorganic peroxides (for example sodium peroxide), which are known from the literature and are commercially available and bleach textile materials at the usual washing temperatures (5 - 95°C).
- Organic peroxides to which preference is given are, for example, mono- or poly-peroxides having at least 3 carbon atoms, preferably from 6 to 20 carbon atoms, in the alkyl chain. Greater preference is given to diperoxydicarboxylates having from 6 to 12 carbon atoms, for example diperoxyperacetates, diperoxypersebacates diperoxyphthalates and diperoxydodecanedioates, emphasis being given especially to the free acids thereof.
- mono- and poly-peroxides especially organic peracids or salts thereof, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic acid, diperoxy- phthalic acid and salts thereof.
- organic peracids or salts thereof such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic acid, diperoxy- phthalic acid and salts thereof.
- the total content of peroxides is preferably from 0.5 to 30% by weight, especially from 1 to 20% by weight and more especially from 1 to 15% by weight.
- a peroxide is used, greater preference is given to a lower limit of 2% by weight, especially 5% by weight.
- inorganic peroxides for example persulfates, perborates, percarbonates and/or persilicates. It will be understood that it is also possible to use mixtures of inorganic and/or organic peroxides.
- the peroxides may be in various crystalline forms and with a varying water content, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.
- the addition of peroxides to the composition is preferably carried out by mixing the components together, for example using a screw metering system and/or a fluidised bed mixer.
- compositions may, in addition to comprising the combination according to the invention, comprise 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 coumarin derivative or a pyrazoline derivative.
- 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 coumarin derivative or a pyrazoline derivative.
- compositions may furthermore comprise one or more auxiliaries.
- auxiliaries 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.
- auxiliaries are added in a total amount of from 0.1 to 20% by weight, especially from 0.5 to 10% by weight, more especially from 0.5 to 5% by weight, based on the total weight of the detergent formulation.
- 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 enzymes 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.
- customary enzymes include, but are by no means limited to, the following: proteases as described in US-B-6242 405, column 14, lines 21 to 32; lipases as described in US-B-6 242405, column 14, lines 33 to 46; amylases as described in US-B-6242 405, column 14, lines 47 to 56; and cellulases as described in US-B-6242 405, column 14, lines 57 to 64.
- the enzymes when used, may be present in a total amount of from 0.01 to 5% by weight, especially from 0.05 to 5% by weight and more especially from 0.1 to 4% by weight, based on the total weight of the detergent formulation.
- 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.
- bleach-activating active substances In addition to using the bleach catalyst according to formula (1) and/or (1'), it is also possible to use further transition metal salts or complexes known as bleach-activating active substances and/or to use conventional bleach activators, that is, compounds that, under the conditions of perhydrolysis, yield unsubstituted or substituted perbenzo- and/or peroxo- carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms.
- conventional bleach activators that is, compounds that, under the conditions of perhydrolysis, yield unsubstituted or substituted perbenzo- and/or peroxo- carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms.
- the customary bleach activators mentioned earlier which contain O- and/or N-acyl groups having the mentioned number of carbon atoms and/or unsubstituted or substituted benzoyl groups, are suitable.
- polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated glycourils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU), acylated triazine derivatives, especially 1 ,5-diacetyl-2,4-dioxohexahydro-1 ,3,5-triazine (DADHT), compounds of formula (8):
- R 2 ⁇ is a sulfonate group, a carboxylic acid group or a carboxylate group and wherein R 22 is a linear or branched (C 7 -C ⁇ 5 )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 pentaacetyl glucose (PAG), sucrose polyacetate (SUPA), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, as well as acetylated, optionally N-alkylated glucamine and gluconolactone.
- 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.
- polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine-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 60000, more especially from 10000 to 50000.
- Such polymers are usually used in a total amount of from 0.01 to 5% by weight, especially from 0.05 to 5% by weight, more especially from 0.1 to 2% by weight, 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).
- the detergent formulations can take a variety of physical forms such as, for example, powder, granule, tablets (tabs) and liquid. Examples thereof include, inter alia, conventional high-performance detergent powders, supercompact high-performance detergent powders and tabs.
- One important physical form is the so-called concentrated granular form, which is added to a washing machine.
- compact or supercompact detergents are so-called compact or supercompact detergents.
- 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% by weight, especially from 0 to 5% by weight, and more especially from 0 to 1 % by weight, 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).
- 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:
- - disintegrators such as cellulose, carboxymethyl cellulose or cross-linked poly(N-vinyl- pyrrolidone);
- 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 to 50% by weight, preferably from 10 to 35% by weight, of water or in the form of a non- aqueous liquid containing no more than 5% by weight, preferably from 0 to 1% by weight, 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, for example 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% to 90% by weight, preferably from 10% to 50% by weight, based on the total weight of the detergent formulation.
- the detergent formulations can also used in so-called "unit liquid dose" form.
- the invention relates also to granules that comprise the catalysts according to the invention and are suitable for incorporation into a powder-form or granular detergent, cleaning or bleaching composition.
- Such granules preferably comprise: a) from 1 to 99% by weight, preferably from 1 to 40% by weight, and especially from 1 to 30% by weight, of at least one metal complex compound of formula (1) and/or (V), b) from 1 to 99% by weight, preferably from 10 to 99% by weight, and especially from 20 to 80% by weight, of a binder, c) from 0 to 20% by weight, especially from 1 to 20% by weight, of an encapsulating material, d) from 0 to 20% by weight of a further additive and e) from 0 to 20% by weight of water.
- binder (b) there come into consideration water-soluble, dispersible or water-emulsifiable anionic dispersants, non-ionic dispersants, polymers and waxes.
- the anionic dispersants used are, for example, commercially available water-soluble anionic dispersants for dyes, pigments etc..
- condensation products of aromatic sulfonic acids and formaldehyde condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenyls or diphenyl oxides and optionally formaldehyde, (mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalenesulfonic acids, sodium salts of polymerised alkylbenzenesulfonic acids, alkylarylsulfonat.es, sodium salts of alkyl polyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acid, sodium salts of alkyl diglycol ether
- Especially suitable anionic dispersants are condensation products of naphthalenesulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, (mono-/di-)- alkylnaphthalenesulfonat.es, polyalkylated polynuclear arylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid, lignosulfonates, oxylignosulfonates and condensation products of naphthalenesulfonic acid with a polychloromethyldiphenyl.
- Suitable non-ionic dispersants are especially compounds having a melting point of, preferably, at least 35°C that are emulsifiable, dispersible or soluble in water, for example the following compounds:
- fatty alcohols having from 8 to 22 carbon atoms, especially cetyl alcohol
- alkylene oxide especially ethylene oxide, wherein some of the ethylene oxide units may have been replaced by substituted epoxides, such as styrene oxide and/or propylene oxide, with higher unsatu rated or saturated monoalcohols, fatty acids, fatty amines or fatty amides having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl phenols, benzyl phenols or alkyl phenols, the alkyl radicals of which have at least 4 carbon atoms;
- substituted epoxides such as styrene oxide and/or propylene oxide
- alkylene oxide especially propylene oxide, condensation products (block polymers);
- sorbitan esters preferably having long-chain ester groups, or ethoxylated sorbitan esters, such as polyoxyethylene sorbitan monolaurate having from 4 to 10 ethylene oxide units or polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene oxide units;
- fatty alcohol polyglycol mixed ethers especially addition products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol of propylene oxide with aliphatic monoalcohols having from 8 to 22 carbon atoms.
- Especially suitable non-ionic dispersants are surfactants of formula
- R 23 is C 8 -C 22 alkyl or C 8 -C ⁇ 8 alkenyl
- R 24 is hydrogen; Ci-dalkyl; a cycloaliphatic radical having at least 6 carbon atoms; or benzyl; "alkylene” is an alkylene radical having from 2 to 4 carbon atoms and n is a number from 1 to 60.
- the substituents R 23 and R 24 in formula (9) are advantageously each the hydrocarbon radical of an unsaturated or, preferably, saturated aliphatic monoalcohol having from 8 to 22 carbon atoms.
- the hydrocarbon radical may be straight-chain or branched.
- R 23 and R 24 are preferably each independently of the other an alkyl radical having from 9 to 14 carbon atoms.
- Aliphatic saturated monoalcohols that may into consideration include natural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and also synthetic alcohols, e.g. 2-ethylhexanol, 1 ,1 ,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethyl- hexanol, trimethylnonyl alcohol, decanol, C 9 -Cn ⁇ xo-alcohol, tridecyl alcohol, isotridecyl alcohol and linear primary alcohols (Alfols) having from 8 to 22 carbon atoms.
- natural alcohols e.g. lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol
- synthetic alcohols e.g. 2-ethylhexanol, 1 ,1 ,3,3-tetramethylbutanol, octan
- Alfols Some examples of such Alfols are Alfol (8-10), Alfol (9-1 1 ), Alfol (10-14), Alfol (12-13) and Alfol (16-18).
- Alfol is a registered trade mark of the company Sasol Limited).
- Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol and oleyl alcohol.
- the alcohol radicals may be present singly or in the form of mixtures of two or more components, e.g. mixtures of alkyl and/or alkenyl groups that are derived from soybean fatty acids, palm kernel fatty acids or tallow oils.
- Alkylene-O chains are preferably bivalent radicals of the formulae
- cycloaliphatic radical examples include cycloheptyl, cyclooctyl and, preferably, cyclohexyl.
- non-ionic dispersants there come into consideration preferably surfactants of formula
- R 2 5 is C 8 -C 22 alkyl
- R 26 is hydrogen or d-dalkyl
- Y ⁇ , Y 2 , Y 3 and Y 4 are each independently of the others hydrogen, methyl or ethyl; n 2 is a number from 0 to 8; and n 3 is a number from 2 to 40.
- non-ionic dispersants correspond to formula 6 ⁇ 7 ⁇ 8
- R 27 is C 9 -C ⁇ 4 alkyl
- R 28 is d-dalkyl
- Y 5 , Ye, Y and Y 8 are each independently of the others hydrogen, methyl or ethyl, one of the radicals Y 5 , Y 6 and one of the radicals Y 7 , Y 8 always being hydrogen; and n 4 and n 5 are each independently of the other an integer from 4 to 8.
- non-ionic dispersants of formulae (9) to (1 1) can be used in the form of mixtures.
- surfactant mixtures there come into consideration non-end-group-terminated fatty alcohol ethoxylates of formula (9), e.g. compounds of formula (9) wherein
- R 23 is C 8 -C 22 alkyl
- R 24 is hydrogen and the alkylene-O chain is the radical -(CH 2 -CH 2 -O)-, and also end-group-terminated fatty alcohol ethoxylates of formula (11).
- non-ionic dispersants of formulae (9), (10) and (11 ) include reaction products of a Ci 0 -Ci 3 fatty alcohol, e.g. a C ⁇ 3 oxo-alcohol, with from 3 to 10 mol of ethylene oxide, propylene oxide and/or butylene oxide and the reaction product of one mol of a C ⁇ 3 fatty alcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide, it being possible for the addition products each to be end-group-terminated with d-C 4 alkyl, preferably methyl or butyl.
- Such dispersants can be used singly or in the form of mixtures of two or more dispersants.
- the granules according to the invention may comprise a water-soluble organic polymer as binder.
- 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, polymethacrylates, polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, polyvinylimidazoles, polyvinyl- pyridine-N-oxides, copolymers of vinylpyrrolidone with long-chain ⁇ -olefins, copolymers 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
- polyethylene glycols carboxymethyl cellulose
- polyacrylamides polyvinyl alcohols
- polyvinylpyrrolidones gelatin
- hydrolysed polyvinyl acetates copolymers of vinylpyrrolidone and vinyl acetate
- polyacrylates copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymethacrylates.
- Suitable water-emulsifiable or water-dispersible binders also include paraffin waxes.
- Encapsulating materials (c) 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.
- additives (d) that come into consideration are, for example, wetting agents, dust removers, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestering agents.
- the preparation of the granules according to the invention is carried out, for example, starting from: a) a solution or suspension with a subsequent drying/shaping step or b) a suspension of the active ingredient in a melt with subsequent shaping and solidification.
- the anionic or non-ionic dispersant and/or the polymer and, optionally, the further additives are dissolved in water and stirred, if desired with heating, until a homogeneous solution is obtained.
- the catalyst according to the invention is then dissolved or suspended in the resulting aqueous solution.
- the solids content of the solution should preferably be at least 30% by weight, especially from 40 to 50% by weight, based on the total weight of the solution.
- the viscosity of the solution is preferably less than 200 mPas.
- the aqueous solution so prepared, comprising the catalyst according to the invention is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) being formed at the same time.
- a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) being formed at the same time.
- Known methods are suitable for producing the granules from the aqueous solution. In principle, both continuous methods and discontinuous methods are suitable. Continuous methods are preferred, especially spray-drying and fluidised bed granulation processes.
- spray-drying processes in which the active ingredient solution is sprayed into a chamber with circulating hot air.
- the atomisation of the solution is effected e.g. using unitary or binary nozzles or is brought about by the spinning effect of a rapidly rotating disc.
- the spray-drying process may be combined with an additional agglomeration of the liquid particles with solid nuclei in a fluidised bed that forms an integral part of the chamber (so-called fluid spray).
- the fine particles ( ⁇ 100 ⁇ m) obtained by a conventional spray-drying process may, if necessary after being separated from the exhaust gas flow, be fed as nuclei, without further treatment, directly into the atomizing cone of the atomiser of the spray-dryer for the purpose of agglomeration with the liquid droplets of the active ingredient.
- the water can rapidly be removed from the solutions comprising the catalyst according to the invention, binder and further additives. It is expressly intended that agglomeration of the droplets forming in the atomising cone, or agglomeration of droplets with solid particles, will take place.
- the granules formed in the spray-dryer are removed in a continuous process, for example by a sieving operation.
- the fines and the oversize particles are either recycled directly to the process (without being redissolved) or are dissolved in the liquid active ingredient formulation and subsequently granulated again.
- a further preparation method is a process in which the polymer is mixed with water and then the catalyst is dissolved/suspended in the polymer solution, thus forming an aqueous phase, the catalyst according to the invention being homogeneously distributed in that phase.
- the aqueous phase is dispersed in a water- immiscible liquid in the presence of a dispersion stabiliser in order that a stable dispersion is formed.
- the water is then removed from the dispersion by distillation, forming substantially dry particles. In those particles, the catalyst is homogeneously distributed in the polymer matrix.
- the granules according to the invention are resistant to abrasion, low in dust, pourable and readily meterable. They can be added directly to a formulation, such as a detergent formulation, in the desired concentration of the catalyst according to the invention.
- the coloured appearance of the granules in the detergent is to be suppressed, this can be achieved, for example, by embedding the granules in a droplet of a whitish meltable substance ("water-soluble wax") or by adding a white pigment (e.g. TiO 2 ) to the granule formulation or, preferably, by encapsulating the granules in a melt consisting, for example, of a water-soluble wax, as described in EP-A-0 323 407, a white solid being added to the melt in order to reinforce the masking effect of the capsule.
- a white pigment e.g. TiO 2
- the catalyst according to the invention is dried in a separate step prior to the melt- granulation and, if necessary, dry-ground in a mill so that all the solids particles are ⁇ 50 ⁇ m in size.
- the drying is carried out in an apparatus customary for the purpose, for example in a paddle dryer, vacuum cabinet orfreeze-dryer.
- the finely paniculate catalyst is suspended in the molten carrier material and homogenised.
- the desired granules are produced from the suspension in a shaping step with simultaneous solidification of the melt.
- the choice of a suitable melt-granulation process is made in accordance with the desired size of granules. In principle, any process which can be used to produce granules in a particle size of from 0.1 to 4 mm is suitable. Such processes are droplet processes (with solidification on a cooling belt or during free fall in cold air), melt- prilling (gas/liquid cooling medium), and flake formation with a subsequent comminution step, the granulation apparatus being operated continuously or discontinuously.
- the coloured appearance of the granules prepared from a melt is to be suppressed in the detergent, in addition to the catalyst it is also possible to suspend in the melt white or coloured pigments which, after solidification, impart the desired coloured appearance to the granules (e.g. titanium dioxide).
- the melt white or coloured pigments which, after solidification, impart the desired coloured appearance to the granules (e.g. titanium dioxide).
- the granules can be covered with or encapsulated in an encapsulating material.
- Methods that come into consideration for such an encapsulation include the customary methods and also encapsulation of the granules by a melt consisting e.g. of a water-soluble wax, as described, for example, in EP-A-0323407, coacervation, complex coacervation and surface polymerisation.
- Encapsulating materials (c) include e.g. water-soluble, water-dispersible or water- emulsifiable polymers and waxes.
- additives (d) there come into consideration, for example, wetting agents, dust removers, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestering agents.
- the metal complex compounds of formula (1) and/or (1') also exhibit a markedly improved bleach-catalysing action on coloured stains occurring, for example, on wall tiles or floor tiles.
- the use of at least one metal complex compound of formula (1) and/or (1 ') as catalyst(s) for reactions with peroxy compounds in cleaning solutions for hard surfaces, especially wall tiles or floor tiles, is therefore of special interest.
- the metal complex compounds of formula (1 ) and/or (1 ') together with peroxy compounds furthermore have excellent antibacterial action.
- the use of at least one metal complex compound of formula (1 ) and/or (V) for killing bacteria or for protecting against bacterial attack is therefore likewise of interest.
- the metal complex compounds of formula (1 ) and/or (1 ') are also outstandingly suitable for selective oxidation in the context of organic synthesis, especially the oxidation of organic molecules, e.g. of olefins to form epoxides. Such selective transformation reactions are required especially in process chemistry.
- the invention accordingly relates also to the use of at least one metal complex compound of formula (1 ) and/or (1 ') in selective oxidation reactions in the context of organic synthesis.
- the hydrochloride obtained in Step 1 is taken up in 300 ml of ethyl acetate and 200 ml of deionised water and rendered neutral with 4N sodium hydroxide solution. After separation of the phases, extraction is carried out twice with 200 ml of ethyl acetate each time. The organic phases are combined, dried over sodium sulfate, filtered and concentrated. 4-Chloropyridine- 2-carboxylic acid ethyl ester is obtained in the form of a brown oil which, if required, can be purified by distillation.
- Example 1 Quatemisation of 2,6-bis[4-(4-methyl-piperazin-1 -yl)-pyrid-2-yl]-pyrimidin-4-ol (ligand PM6) with methyl iodide to form ligand PM7
- Example 12 4.6-Di-pvrid-2-vl- ⁇ .3.5.triazin-2-ol (ligand TZ1 )
- the mixture is rendered neutral with 2N sulfuric acid, and the crude product is filtered off and recrystallised from 55 ml of methanol, yielding 4,6-di-pyrid-2-yl-[1 ,3,5]triazin- 2-ol in the form of a white solid.
- Example 14 Manganese complex with 6-[4-(4-methyl-piperazin-1 -yl)-pyrid-2-yl]-2-pyrid-2-yl- pyrimidin-4-ol (ligand PM2)
- Example 15 Manganese complex with quaternised 6-[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-
- 7.5 g of white cotton fabric and 2.5 g of tea-stained cotton fabric are treated in 80 ml of washing liquor.
- the liquor contains a standard detergent (I EC 60456 A * ) in a concentration of 7.5 g/l.
- the hydrogen peroxide concentration is 8.6 mmol/litre.
- the catalyst concentration (1 :1 complex of manganese(ll) chloride tetrahydrate with the ligand in question, prepared in methanol or water, as decribed above) is 50 ⁇ mol/l.
- the increase in lightness DY difference in lightness according to CIE
- Application Example 2 (Cleaning performance on soiled surfaces) A filter paper stained with melanin, a pigment typically responsible for the inherent colour of mould, is wetted at room temperature with a solution containing 0.4% sodium hydrogen carbonate, 0.5% sodium carbonate, 0.2% of a non-ionic surfactant (fatty alcohol polyethylene glycol ether), 2% hydrogen peroxide and, as desired, 100 ppm of a catalyst, prepared as described in Application Example 1. After 20 minutes, the filter paper is washed with water and dried at room temperature. The lightness Y of the filter paper before and after the test is determined by means of reflectance spectroscopy (according to CIE) and the bleaching performance is determined as the difference between the two measurements (DY) (Table 2). In order to assess the bleaching performance of the catalysts, a control experiment is carried out with the above-mentioned solution but without catalyst.
- a non-ionic surfactant fatty alcohol polyethylene glycol ether
- test solution containing 0.1 M carbonate buffer (pH 10) and alkali metal/lignin solution (Aldrich No. 37,095-9; 5 ml of a 10 g/l solution).
- the absorption at 425 nm wavelength is determined spectrophotometrically, after
- the Kappa number of the pulp after the treatment is determined according to TAPPI T236 om-99 and is 17.5.
- the Kappa number of the pulp in a control experiment without catalyst is 19.6. The use of the catalyst thus results in a further reduction of the Kappa number.
- Application Example 7 (Action as a catalyst for dye transfer inhibition (DTI)) According to this application, the object is to prevent redeposition of migrating dyes, especially in washing liquors.
- DTI dye transfer inhibition
- the liquor comprises a standard detergent (IEC 60456 A * ) in a concentration of 7.5 g/l, 8.6 mmol/l of hydrogen peroxide and a solution of the test dye Reactive Blue 238 (6 mg/l of the 100% formulation).
- the catalyst solution is prepared in advance by mixing an aqueous solution of manganese(ll) chloride tetrahydrate or iron(ll) chloride and the appropriate ligand. There is thus established a catalyst concentration of 50 ⁇ mol/l in the liquor.
- the washing process is carried out for 30 minutes at 40°C in a steel beaker in a LINITEST apparatus. To test the activity of the catalysts, the DTI activity is determined.
- the reflection spectra of the samples are measured using a SPECTRAFLASH 2000 and converted into lightness values (D65/10) in accordance with a standard CIE procedure. The results are shown in Table 6 below.
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Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
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EP03769428A EP1556467B1 (en) | 2002-10-30 | 2003-10-21 | Use of metal complex compounds as oxidation catalysts |
MXPA05004167A MXPA05004167A (en) | 2002-10-30 | 2003-10-21 | Use of metal complex compounds as oxidation catalysts. |
US11/520,398 US7291584B2 (en) | 2002-10-30 | 2003-10-21 | Use of metal complex compounds as oxidation catalysts |
CN2003801026668A CN1711347B (en) | 2002-10-30 | 2003-10-21 | Use of metal complex compounds as oxidation catalysts |
JP2004547539A JP4538797B2 (en) | 2002-10-30 | 2003-10-21 | Use of metal complex compounds as oxidation catalysts |
BR0315869-1A BR0315869A (en) | 2002-10-30 | 2003-10-21 | Use of metal complex compounds as oxidation catalysts |
DE60306672T DE60306672T2 (en) | 2002-10-30 | 2003-10-21 | USE OF METAL COMPLEX COMPOUNDS AS OXIDATION CATALYSTS |
US10/531,906 US7138363B2 (en) | 2002-10-30 | 2003-10-21 | Use of metal complex compounds as oxidation catalysts |
AU2003278117A AU2003278117B2 (en) | 2002-10-30 | 2003-10-21 | Use of metal complex compounds as oxidation catalysts |
US11/901,660 US7612010B2 (en) | 2002-10-30 | 2007-09-18 | Use of metal complex compounds as oxidation catalysts |
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US (3) | US7138363B2 (en) |
EP (1) | EP1556467B1 (en) |
JP (1) | JP4538797B2 (en) |
KR (1) | KR101004084B1 (en) |
CN (1) | CN1711347B (en) |
AT (1) | ATE332356T1 (en) |
AU (1) | AU2003278117B2 (en) |
BR (1) | BR0315869A (en) |
DE (1) | DE60306672T2 (en) |
ES (1) | ES2268440T3 (en) |
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WO (1) | WO2004039934A1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2005068075A1 (en) * | 2004-01-12 | 2005-07-28 | Ciba Specialty Chemicals Holding Inc. | Use of a composition comprising metal complex compounds and polyphosphonates as catalysts for oxidations |
WO2005068074A2 (en) * | 2004-01-12 | 2005-07-28 | Ciba Specialty Chemicals Holding Inc. | Use of metal complex compounds comprising pyridine pryimidine or s-triazne derived ligands as catalysts for oxidations with organic peroxy acids and/or precursors of organic peroxy acid and h2o2 |
WO2005099711A1 (en) * | 2004-04-13 | 2005-10-27 | Icagen, Inc. | Polycyclic pyrimidines as potassium ion channel modulators |
WO2005105303A1 (en) * | 2004-04-29 | 2005-11-10 | Ciba Specialty Chemicals Holding Inc. | Use of metal complexes having bispyridylpyrimidine or bispyridyltriazine ligands as catalysts for reactions with peroxy compounds for bleaching coloured stains on hard surfaces |
WO2005116181A1 (en) * | 2004-05-17 | 2005-12-08 | Henkel Kommanditgesellschaft Auf Aktien | Bleach reinforcer combination for use in washing and cleaning agents |
WO2007090461A1 (en) * | 2006-02-06 | 2007-08-16 | Ciba Holding Inc. | Use of metal complex compounds as oxidation catalysts |
EP1840198A1 (en) * | 2006-03-30 | 2007-10-03 | Unilever Plc | Bleaching composition |
EP2103735A1 (en) | 2008-03-18 | 2009-09-23 | Unilever PLC | Catalytic bleaching of substrates |
WO2019113926A1 (en) * | 2017-12-15 | 2019-06-20 | Rhodia Operations | Composition containing lanthanide metal complex |
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US7259122B1 (en) * | 2004-08-30 | 2007-08-21 | John Lombardi | Chemically-resistant shelter coating |
JP5270678B2 (en) * | 2007-07-23 | 2013-08-21 | ビーエーエスエフ ソシエタス・ヨーロピア | Use of metal complex compounds as oxidation catalysts |
CN103174006A (en) * | 2011-11-24 | 2013-06-26 | 东华大学 | Application of bipyridyl pyrimidine metal complex to low-temperature scouring and bleaching auxiliary for textiles |
CN107617418A (en) * | 2016-07-16 | 2018-01-23 | 天津师范大学 | Application of thiocyanate radical Co (II) complexs based on 3 (oxadiazole of 5 methyl 1,3,4) pyridines in dyestuff is adsorbed |
JP7145802B2 (en) * | 2019-03-27 | 2022-10-03 | 大阪ガスケミカル株式会社 | Method for producing 2-amino-1,3,5-triazine compound |
CN115999640B (en) * | 2023-02-06 | 2024-05-17 | 广西大学 | Preparation method and application of bagasse cellulose-based heterojunction organic composite photocatalyst |
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PL350514A1 (en) * | 1999-04-01 | 2002-12-16 | Unilever Nv | Composition and method for bleaching a substrate |
US7161005B2 (en) * | 2001-04-30 | 2007-01-09 | Ciba Specialty Chemicals Corporation | Use of metal complex compounds as oxidation catalysts |
-
2003
- 2003-10-21 AU AU2003278117A patent/AU2003278117B2/en not_active Ceased
- 2003-10-21 WO PCT/EP2003/011636 patent/WO2004039934A1/en active IP Right Grant
- 2003-10-21 US US10/531,906 patent/US7138363B2/en not_active Expired - Fee Related
- 2003-10-21 JP JP2004547539A patent/JP4538797B2/en not_active Expired - Fee Related
- 2003-10-21 BR BR0315869-1A patent/BR0315869A/en not_active Application Discontinuation
- 2003-10-21 CN CN2003801026668A patent/CN1711347B/en not_active Expired - Fee Related
- 2003-10-21 AT AT03769428T patent/ATE332356T1/en not_active IP Right Cessation
- 2003-10-21 KR KR1020057007419A patent/KR101004084B1/en not_active IP Right Cessation
- 2003-10-21 MX MXPA05004167A patent/MXPA05004167A/en active IP Right Grant
- 2003-10-21 EP EP03769428A patent/EP1556467B1/en not_active Expired - Lifetime
- 2003-10-21 US US11/520,398 patent/US7291584B2/en not_active Expired - Fee Related
- 2003-10-21 DE DE60306672T patent/DE60306672T2/en not_active Expired - Lifetime
- 2003-10-21 ES ES03769428T patent/ES2268440T3/en not_active Expired - Lifetime
-
2007
- 2007-09-18 US US11/901,660 patent/US7612010B2/en not_active Expired - Fee Related
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US5453450A (en) * | 1993-06-16 | 1995-09-26 | Minnesota Mining And Manufacturing Company | Stabilized curable adhesives |
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WO2000060043A1 (en) * | 1999-04-01 | 2000-10-12 | Unilever Plc | Composition and method for bleaching a substrate |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2005068074A2 (en) * | 2004-01-12 | 2005-07-28 | Ciba Specialty Chemicals Holding Inc. | Use of metal complex compounds comprising pyridine pryimidine or s-triazne derived ligands as catalysts for oxidations with organic peroxy acids and/or precursors of organic peroxy acid and h2o2 |
WO2005068074A3 (en) * | 2004-01-12 | 2006-05-18 | Ciba Sc Holding Ag | Use of metal complex compounds comprising pyridine pryimidine or s-triazne derived ligands as catalysts for oxidations with organic peroxy acids and/or precursors of organic peroxy acid and h2o2 |
WO2005068075A1 (en) * | 2004-01-12 | 2005-07-28 | Ciba Specialty Chemicals Holding Inc. | Use of a composition comprising metal complex compounds and polyphosphonates as catalysts for oxidations |
US7560464B2 (en) | 2004-04-13 | 2009-07-14 | Icagen, Inc. | Polycyclic pyrimidines as potassium ion channel modulators |
WO2005099711A1 (en) * | 2004-04-13 | 2005-10-27 | Icagen, Inc. | Polycyclic pyrimidines as potassium ion channel modulators |
WO2005105303A1 (en) * | 2004-04-29 | 2005-11-10 | Ciba Specialty Chemicals Holding Inc. | Use of metal complexes having bispyridylpyrimidine or bispyridyltriazine ligands as catalysts for reactions with peroxy compounds for bleaching coloured stains on hard surfaces |
WO2005116181A1 (en) * | 2004-05-17 | 2005-12-08 | Henkel Kommanditgesellschaft Auf Aktien | Bleach reinforcer combination for use in washing and cleaning agents |
WO2007090461A1 (en) * | 2006-02-06 | 2007-08-16 | Ciba Holding Inc. | Use of metal complex compounds as oxidation catalysts |
EP1840198A1 (en) * | 2006-03-30 | 2007-10-03 | Unilever Plc | Bleaching composition |
EP2103735A1 (en) | 2008-03-18 | 2009-09-23 | Unilever PLC | Catalytic bleaching of substrates |
WO2019113926A1 (en) * | 2017-12-15 | 2019-06-20 | Rhodia Operations | Composition containing lanthanide metal complex |
CN111479913A (en) * | 2017-12-15 | 2020-07-31 | 罗地亚经营管理公司 | Compositions containing lanthanide metal complexes |
US11441105B2 (en) | 2017-12-15 | 2022-09-13 | Rhodia Operations | Composition containing lanthanide metal complex |
Also Published As
Publication number | Publication date |
---|---|
ATE332356T1 (en) | 2006-07-15 |
EP1556467B1 (en) | 2006-07-05 |
US20080081908A1 (en) | 2008-04-03 |
US20060052265A1 (en) | 2006-03-09 |
US7612010B2 (en) | 2009-11-03 |
ES2268440T3 (en) | 2007-03-16 |
AU2003278117B2 (en) | 2009-07-30 |
BR0315869A (en) | 2005-09-27 |
KR101004084B1 (en) | 2010-12-27 |
US7291584B2 (en) | 2007-11-06 |
MXPA05004167A (en) | 2005-06-08 |
JP4538797B2 (en) | 2010-09-08 |
CN1711347A (en) | 2005-12-21 |
US7138363B2 (en) | 2006-11-21 |
DE60306672T2 (en) | 2007-06-28 |
US20070032656A1 (en) | 2007-02-08 |
AU2003278117A1 (en) | 2004-05-25 |
CN1711347B (en) | 2010-05-26 |
KR20050065636A (en) | 2005-06-29 |
JP2006504517A (en) | 2006-02-09 |
EP1556467A1 (en) | 2005-07-27 |
DE60306672D1 (en) | 2006-08-17 |
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