METAL COMPLEXES, AND DISHWASHING PRODUCTS CONTAINING SAME

Abstract

The invention relates to dishwashing products that contain metal complexes of the general formula (I),

(A.sup.q+).sub.p[M.sup.n+L.sup.m?](X.sup.o?).sub.r(I)

wherein q is 1 or 2 and A.sup.q+ represents a cation, selected from alkali metal cations with q=1, alkaline earth cations with q=2 and ammonium ions with q=1, M.sup.n+ represents an aluminum ion, a transition metal ion or a lanthanoid metal ion, n is a number from 1 to 5, L represents a ligand of formula

##STR00001##

in which each R independently of each other is OH or O.sup.?, m represents a number from 0 to 2, X.sup.o? represents an anion selected from F.sup.?, Cl.sup.?, Br.sup.?, I.sup.?, OH.sup.?, HSO.sub.3.sup.+, SO.sub.3.sup.2?, SO.sub.4.sup.2?, HSO.sub.4.sup.?, NO.sub.2.sup.?, NO.sub.3.sup.?, PO.sub.4.sup.3?, HPO.sub.4.sup.2?, H.sub.2PO.sub.4.sup.?, BF.sub.4.sup.?, PF.sub.6.sup.?, ClO.sub.4.sup.?, acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methane sulfonate, methyl sulfate, p-toluene sulfonate, p-toluene sulfate and succinate, and o is a number from 1 to 3, and p and r independently of each other represent a number from 0 to 4, with the proviso that the sum of n and the product of p and q is equal to the sum of m and the product of r and o.

Claims

1. A metal complex of general formula (I),
(A.sup.q+).sub.p[M.sup.n+L.sup.m?](X.sup.o?).sub.r(I) wherein q is 1 or 2 and A.sup.q+ represents a cation, selected from alkali metal cations with q 1, alkaline earth cations with q=2 and ammonium ions with q=1, M.sup.n+ represents an aluminum ion, a transition metal ion or a lanthanoid metal ion, n is a number from 1 to 5, L represents a ligand of formula ##STR00006## in which each R independently represents OH or O.sup.?, m represents a number from 0 to 2, X.sup.o? represents an anion selected from F.sup.?, Cl.sup.?, Br.sup.?, I.sup.?, OH.sup.?, HSO.sub.3.sup.?, SO.sub.3.sup.2?, SO.sub.4.sup.2?, HSO.sub.4.sup.?, NO.sub.2.sup.?, NO.sub.3.sup.?, PO.sub.4.sup.3?, HPO.sub.4.sup.2?, H.sub.2PO.sub.4.sup.?, BF.sub.4.sup.?, PF.sub.6.sup.?, ClO.sub.4.sup.?, acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methane sulfonate, methyl sulfate, p-toluene sulfonate, p-toluene sulfate and succinate, and o represents a number from 1 to 3, and p and r represent, independently of one another, a number from 0 to 4, with the proviso that the sum of n and the product of p and q is equal to the sum of m and the product of r and o.

2. A dishwashing detergent, in particular an automatic dishwashing detergent, containing a metal complex of the general formula (I),
(A.sup.q+).sub.p[M.sup.n+L.sup.m?](X.sup.o?).sub.r(I) wherein q is 1 or 2 and A.sup.q+ represents a cation, selected from alkali metal cations with q 1, alkaline earth cations with q=2 and ammonium ions with q=1, M.sup.n+ represents an aluminum ion, a transition metal ion or a lanthanoid metal ion, n is a number from 1 to 5, L represents a ligand of formula ##STR00007## in which each R independently of each other is OH or O.sup.?, m represents a number from 0 to 2, X.sup.o? represents an anion selected from F.sup.?, Cl.sup.?, Br.sup.?, I.sup.?, OH.sup.?, HSO.sub.3, SO.sub.3.sup.2?, SO.sub.4.sup.2?, HSO.sub.4.sup.?, NO.sub.2.sup.?, NO.sub.3.sup.?, PO.sub.4.sup.3?, HPO.sub.4.sup.2?, H.sub.2PO.sub.4.sup.?, BF.sub.4.sup.?, PF.sub.6.sup.?, ClO.sub.4.sup.?, acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methane sulfonate, methyl sulfate, p-toluene sulfonate, p-toluene sulfate and succinate, and o is a number from 1 to 3, and p and r independently of each other represent a number from 0 to 4, with the proviso that the sum of n and the product of p and q is equal to the sum of m and the product of r and o.

3. A use of a metal complex of the general formula (I),
(A.sup.q+).sub.p[M.sup.n+L.sup.m?](X.sup.o?).sub.r(I) wherein q is 1 or 2 and A.sup.q+ represents a cation, selected from alkali metal cations with q=1, alkaline earth cations with q=2 and ammonium ions with q=1, M.sup.n+ represents an aluminum ion, a transition metal ion or a lanthanoid metal ion, n is a number from 1 to 5, L represents a ligand of formula ##STR00008## in which each R independently represents OH or O.sup.?, m represents a number from 0 to 2, X.sup.o? represents an anion selected from F.sup.?, Cl.sup.?, Br.sup.?, I.sup.?, OH.sup.?, HSO.sub.3.sup.?, SO.sub.3.sup.2?, SO.sub.4.sup.2?, HSO.sub.4.sup.?, NO.sub.2.sup.?, NO.sub.3.sup.?, PO.sub.4.sup.3?, HPO.sub.4.sup.2?, H.sub.2PO.sub.4.sup.?, BF.sub.4.sup.?, PF.sub.6.sup.?, ClO.sub.4.sup.?, acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methane sulfonate, methyl sulfate, p-toluene sulfonate, p-toluene sulfate and succinate, and o represents a number from 1 to 3, and p and r represent, independently of one another, a number from 0 to 4, with the proviso that the sum of n and the product of p and q is equal to the sum of m and the product of r and o, or of a dishwashing detergent containing such a complex in an automatic dishwashing method for removing soiling.

4. An automatic dishwashing method in which a metal complex of the general formula (I),
(A.sup.q+).sub.p[M.sup.n+L.sup.m?](X.sup.o?).sub.r(I) in which q represents 1 or 2 and A.sup.q+ represents a cation selected from alkali metal cations where q=1, alkaline earth cations where q=2, and ammonium ions where q=1, M.sup.n+ represents an aluminum ion, a transition metal ion or a lanthanide metal ion, n represents a number from 1 to 5, L represents a ligand of the formula (II), ##STR00009## in which each R independently represents OH or O.sup.?, m represents a number from 0 to 2, X.sup.o? represents an anion selected from F.sup.?, Cl.sup.?, Br.sup.?, I.sup.?, OH.sup.?, HSO.sub.3, SO.sub.3.sup.2?, SO.sub.4.sup.2?, HSO.sub.4.sup.?, NO.sub.2.sup.?, NO.sub.3.sup.?, PO.sub.4.sup.3?, HPO.sub.4.sup.2?, H.sub.2PO.sub.4.sup.?, BF.sub.4.sup.?, PF.sub.6.sup.?, ClO.sub.4.sup.?, acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methane sulfonate, methyl sulfate, p-toluene sulfonate, p-toluene sulfate and succinate, and o represents a number from 1 to 3, and p and r represent, independently of one another, a number from 0 to 4, with the proviso that the sum of n and the product of p and q is equal to the sum of m and the product of r and o, or a dishwashing detergent containing such a complex is used.

5. The complex according to claim 1, characterized in that M.sup.n+ is selected from Al.sup.3+, Ti.sup.4+, Y.sup.3+, Zr.sup.4+, Ce.sup.3+, Ce.sup.4+, Sc.sup.3+, Yb.sup.3+ and mixtures thereof.

6. The detergent according to claim 2, characterized in that the detergent contains 0.001 wt. % to 10 wt. %, in particular 0.01 wt. % to 3 wt. % of the metal complex of the formula (III).

7. The detergent according to claim 2, characterized in that M.sup.n+ is selected from Al.sup.3+, Ti.sup.4+, Y.sup.3+, Zr.sup.4+, Ce.sup.3+, Ce.sup.4+, Sc.sup.3+, Yb.sup.3+ and mixtures thereof.

8. The use according to claim 3, characterized in that M.sup.n+ is selected from Al.sup.3+, Ti.sup.4+, Y.sup.3+, Zr.sup.4+, Ce.sup.3+, Ce.sup.4+, Sc.sup.3+, Yb.sup.3+ and mixtures thereof.

9. The method according to claim 4, characterized in that M.sup.n+ is selected from Al.sup.3+, Ti.sup.4+, Y.sup.3+, Zr.sup.4+, Ce.sup.3+, Ce.sup.4+, Sc.sup.3+, Yb.sup.3+ and mixtures thereof.

10. The detergent according to claim 2, characterized in that the detergent contains 0.001 wt. % to 10 wt. %, in particular 0.01 wt. % to 3 wt. % of the metal complex of the formula (III).

11. The use according to claim 3, characterized in that the detergent contains 0.001 wt. % to 10 wt. %, in particular 0.01 wt. % to 3 wt. % of the metal complex of the formula (III).

12. The method according to claim 4, characterized in that the detergent contains 0.001 wt. % to 10 wt. %, in particular 0.01 wt. % to 3 wt. % of the metal complex of the formula (III).

Description

EXAMPLES

Example 1: Synthesis of 1,7-dioxa-4,10-diazacyclododecane-4,10-di(methyl(phenol)) (L1)

[0052] A solution of 3 g (9.96 mmol) of 2-(bromomethyl)phenyl-tert-butyldimethylsilyl ether in 10 ml of N,N-dimethylacetamide was slowly added via a syringe pump (7 ml/h) to a solution of 603 mg (3.3 mmol) of 1,7-dioxa-4,10-diazacyclododecane and 908 mg (10.96 mmol) of sodium acetate in 180 ml of N,N-dimethylacetamide cooled to ?8? C. to ?5? C. in an ice/NaCl bath. The reaction mixture was stirred for 23 hours, heated to room temperature and stirred for another 24 hours at room temperature. The mixture was then heated to 50? C. for 5 hours, then cooled again to room temperature and concentrated under reduced pressure (70? C., 15 mbar). The remaining residue was taken up in 75 ml of CH.sub.2C.sub.12, extracted 3 times with 100 ml of aqueous 1 N NaOH, then washed 4 times with 120 ml of water and dried over MgSO.sub.4. The CH.sub.2Cl.sub.2 phase was then extracted 2 times with 100 ml of saturated NH.sub.4Cl solution, then washed 4 times with 120 ml of water, then dried over MgSO.sub.4, and the solvent was removed under reduced pressure. This resulted in 740 mg of L1 as a white solid.

Example 2: Synthesis of the Sc (III) Complex of 1,7-dioxa-4,10-diazacyclododecane-4,10-di(methyl(phenol))

[0053] Under an N.sub.2 atmosphere, a solution of 126 mg (0.82 mmol) of ScCl.sub.3 in 3 ml of methanol was slowly added to a solution heated to 65? C. of 3.7 ml 0.5 M KOH in methanol and 320 mg (0.83 mmol) of the ligand L1 produced in Example 1 in 27 ml of methanol. The reaction mixture was stirred for 48 hours at 65? C. and then cooled to room temperature. The resulting precipitate was filtered off and discarded. The filtrate was concentrated under reduced pressure to half its volume and stored in an ice cabinet (?22? C.) for 6 days. The resulting precipitate was filtered off and discarded. The filtrate was concentrated under reduced pressure to half its volume and stored in an ice cabinet (?22? C.) overnight. The resulting precipitate was filtered off and discarded. The filtrate was concentrated to dryness and dried under reduced pressure. This resulted in 347 mg of the complex P1 as an orange-yellow solid.

Example 3: Hydrolysis of Protein Soiling

[0054] The hydrolysis of protein dirt was investigated using degradation of bovine serum albumin (BSA). For this purpose, an aqueous BSA solution was mixed with the complex P1 produced in Example 2, so that the concentration of BSA was 0.02 mM and the concentration of the complex was 2 mM, incubated at 60? C. and pH 9 (adjusted with NaOH and HCl) for 24 hours. The incubated material was then examined with the known method of SDS-PAGE with regard to the intensity of the band to be assigned to BSA. BSA incubated under the same conditions without the addition of complexes served as reference. The intensity values given in the following table are relative values based on the intensity of the band of the reference at t=24 h. The values show that the albumin band has decreased in the presence of the substance according to the invention from Example 1:

TABLE-US-00001 Sample Intensity Reference, 24 h incubation 1.0 BSA + complex P1, 24 h incubation 0.84