Bleaching-active metal complexes

Details Bleaching-active metal complexes Bleaching-active metal complexes

2000-09-08

2003-04-08

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Unsubstituted hydrocarbyl chain between the ring and the -c-...

C510S218000, C510S311000, C510S372000, C510S376000, C252S186330, C544S004000, C544S064000, C544S181000, C544S225000, C546S002000, C548S402000, C548S101000, C548S108000, C548S955000, C549S003000, C549S206000, C549S208000

Reexamination Certificate

active

06545147

ABSTRACT:

BACKGROUND OF THE INVENTION
It is known that the bleaching power of peroxide bleaches, such as hydrogen peroxide, perborates, percarbonates, persilicates and perphosphates, in detergents and cleaners, and hence their efficiency in removing tea, coffee, fruit or red wine stains, is only fully attained at temperatures of significantly greater than 60° C. To improve the bleaching effect, which is greatly reduced at, especially, temperatures below 60° C., it is possible to use compounds to activate the peroxide bleaches. A number of transition metal salts or corresponding complexes with mostly chelating compounds have been proposed for this purpose, although the effectiveness of a metal or of a specific combination of transition metal and complex ligand cannot be predicted.
WO 96 06154 and EP 458 397 claim metal complexes with a high activation potential. A disadvantage of the types of complex described therein is that they considerably damage the fibers and colors of textiles. J. Am. Chem. Soc., 1989, 111, 5102-5114 describes the crystalline structure of a bicyclic manganese complex containing a bridging 2,6-bis(1,4,7-triazacyclononan-1-ylmethyl)4-methylphenoxide ligand, two bridging acetate groups and two perchlorate anions, where the oxidation states of the two metal centers are mixed, and one manganese atom is ascribed the oxidation number II and the second manganese atom the oxidation number III. The applications-related relevance of this compound has hitherto not been reported.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention therefore provides unknown compounds of the formula I which intensify the bleaching power of peroxo compounds, even at low temperatures, without attacking the textile fibers or textile dyes
[L
n
M
m
X
p
]
Z
Y
q
  formula I
where
M is manganese in oxidation state II, III, IV and/or V, iron in oxidation state II and/or III or cobalt in oxidation state II and/or III,
X is a coordination group or bridging group,
Y is a counterion in the corresponding stoichiometric amount to balance an existing charge z, where
z as the charge of the metal complex can be positive, zero or negative, n and m, independently of one another, are integers from 1 to 4,
p is an integer from 0 to 15,
q is z/charge of Y,
L is an organic ligand of the general formula II
where
R
1
and R
2
, independently of one another, are hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyl or alkinyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group which may also be substituted,
each D, independently of one another, is NR
3
, O, PR
3
or S, where R
3
is an alkyl group having 1 to 6 carbon atoms, an alkenyl or alkinyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group which may also be substituted,
each E, independently of one another, is N, P or C(R
1
) with the meanings given above for R
1
,
t is a number from 0 to 6, s is a number from 1 to 5 and u is a number from 1 to4,
A is a C
3
- to Cg-cycloalkyl, phenyl, 1,1′-biphenyl, naphthyl, anthracenyl or pyridinyl radical,
each R
4
, independently of one another, is hydrogen, a C
1
- to C
6
-alkyl group, a C
1
- to C
3
-alkoxy group, a C
3
- to C
10
-cycloalkyl group or a phenyl group which may also be substituted,
v is a number from 0 to 15,
K is a group coordinating to at least one of the metal centers M and is of the type —O, —OR, —S, —SR, —NR
2
, —NR, —PR
2
or —PR, where R is hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl or alkinyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group which may also be substituted, X is an anion of the following formulae:
F
−
, Cl
−
, Br
−
, SCN
−
, OH
−
, O
2
2−
, O
2−
, O
2
−
, R
10
OO
31
, H
2
O, HS
31
, CN
−
, OCN
−
, S
2−
,N
3
−
, NH
3
, NR
10
3
, NR
10
2
, R
10
O
−
, R
10
COO
−
, R
10
SO
3
−
and R
10
SO
4
31
, where R
10
is in each case hydrogen, C
1
- to C
8
-alkyl, C
3
- to C
8
-cycloalkyl or C
6
- to C
18
-aryl, and
Y
if z is positive, is an anion of the following formulae: F
−
, Cl
−
, Br
−
, NO
3
−
, ClO
4
−
, SCN
−
, PF
6
−
, R
10
SO
4
−
, R
10
COO
−
, R
10
SO
3
−
, BF
4
−
, BPh
4
−
and SO
4
2−
and
if z is negative, is a cation of the following formulae: Li
+
, Na
+
, K
+
, Mg
2+
, Ca
2+
, Al
3+
, NH
4
+
, R
10
NH
3
30
, R
10
2
NH
2
+
, R
10
3
NH
+
and R
10
4
N
+
, where R
10
has the meaning given above.
Preference is given to compounds in which D is NR
3
, E is nitrogen, R
1
and R
2
are hydrogen, s is a number from 1 to 3, t is a number from 1 to 4 and K is a group of the type —O, —OR, —S or —NR
2
, and the other symbols have the meanings given above.
Particular preference is given to compounds in which A is a phenyl or C
3
- C
9
-cycloalkyl group, m is a number from 1 to 3 and n is a number from 1 to 2. If individual symbols in the formula II are a substituted phenyl group, such phenyl groups can be substituted by one to three groups of the following type: C
1
- C
4
-alkyl, C
1
-C
4
-alkoxy, halogen atoms, substituted or unsubstituted amino or ammonium groups, sulfo groups, carboxyl groups or groups of the formula —(CH
2
)
r
-COOH, —(CH
2
)
r
-SO
3
H, —(CH
2
)
r
-PO
3
H
2
, —(CH
2
)
1
—OH, where r is an integer from 0 to 4 and I is an integer from 1 to 4, and said acid groups can also be in salt form.
The novel transition metal complexes according to formula I are synthesized from a heterocyclic bridging ligand L according to formula II, e.g. 2,6-bis(4,7-dimethyl-1,4,7-triazacyclonon-1-ylmethyl)-4-methylphenol, dissolved in a polar solvent, for example an alcohol, to which, in the molar ratio 1:2, a transition metal compound, e.g. manganese(ll) acetate tetrahydrate, and the required amount of a compound comprising the counterion Y, e.g. KPF
6,
is added at a pH between 7 and 11 in a temperature range between 0 to 100° C., preferably 25 to 50° C. The bridging ligands of the formula II present in the complexes according to the invention can, for example, be synthesized analogously to the synthesis described in J. Am. Chem. Soc. 1994, 116, 22, 10334-10335, by reacting a heterocyclic compound of the type of the formula Ill
having the abovementioned definitions for D, E, R
1
, R
2
, t and s, for example 1,4-dimethyl-1,4,7-triazacyclononane, dissolved in a polar solvent, preferably an alcohol, in the presence of equimolar amounts of a base, preferably triethylamine, with a compound of the type Z-(CR
1
CR
2
)
u
-A(K)(R
4
)
v
-(CR
1
CR
2
)
U
-Z with the abovementioned definitions for R
1
, R
2
, R
4
, A, K, u and v, where Z is chlorine, bromine, iodine or another leaving group, in the molar ratio 2 to 1 in the temperature range from −30 to 80° C., preferably −10 to 50° C., in the course of 10 to 120 hours.
The novel polycyclic complexes of the formula I are highly suitable as bleaching and oxidation catalysts, in particular in detergents and cleaners, and in the bleaching of textiles and paper. Particular emphasis should be placed here on textile detergents in the form of pulverulent detergents or as liquid formulations, and dishwashing detergents. An advantage of the bleaching catalysts according to the invention is their stability to hydrolysis and oxidation and also their catalytic effect even at low temperatures. In such formulations, they not only improve the bleaching action of hydrogen peroxide, but also of organic and inorganic peroxy compounds.
The present invention accordingly also provides a method of bleaching soiled substrates in which the soiled substrate is brought into contact in an aqueous bleaching liquor with a peroxy compound and an effective amount of one or more of the novel metal complexes according to formula I, where R
3
can also be hydrogen and A can also be carbon, as bleaching catalyst

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