Manganese complexes of salen ligands and the use thereof

Details Manganese complexes of salen ligands and the use thereof Manganese complexes of salen ligands and the use thereof

2001-09-05

2004-02-10

Delcotto, Gregory (Department: 1751)

Cleaning compositions for solid surfaces, auxiliary compositions

Cleaning compositions or processes of preparing

With oxygen or halogen containing chemical bleach or oxidant...

C510S220000, C510S221000, C510S224000, C510S372000, C510S378000, C252S186290, C252S186330, C502S200000, C502S324000

Reexamination Certificate

active

06689733

ABSTRACT:

The present invention relates to novel manganese complexes of salen ligands and to the use thereof as catalysts that enhance the action of peroxy compounds in washing, cleaning and disinfecting processes. The invention furthermore relates to formulations used in such processes that comprise the manganese complexes and peroxy compounds, and also to the novel ligands and to processes for the preparation thereof.
A number of manganese complexes of the salen type are already known to be suitable catalysts for oxidations that use peroxy compounds, especially within the context of washing procedures. Also, certain other manganese complexes have already been described as having a pronounced bleaching action on dirt and dyes in washing liquors. There is nevertheless still a need for further compounds having improved action and/or a broader field of application, but such compounds should not cause any appreciable damage to fibres or colours when used on textile material.
It has now been found that certain novel manganese complexes of the salen type as catalysts largely meet the required conditions. They enhance the action of peroxy compounds in a very wide variety of applications, substantially without damage occurring to fibres or colours. Surprisingly, when the manganese complexes according to the invention are employed in aqueous solution together with peroxy compounds, the enhanceed action occurs in the following applications:
a) the bleaching of stains or soiled areas on textile material within the context of a washing procedure,
b) the inhibition of migrating dyes being redeposited when textile material is washed,
c) the cleaning of hard surfaces, especially crockery or glass,
d) the cleaning of hard surfaces, especially glazed tiles or floor tiles, especially for the removal of stains that have formed as a result of the action of molds (mold stains), and
e) the use of washing and cleaning solutions that have an antibacterial activity.
The present invention accordingly relates to compounds of formula
wherein
n is 0, 1 or 2,
m is 1 or 2,
A is an anion;
Y is a linear or branched alkylene radical of formula —[C(R
5
)
2
]
r
— wherein r is an integer of from 1 to 8 and the R
5
radicals are each independently of the others hydrogen or C
1
-C
4
alkyl; —CX═CX— wherein X is cyano, linear or branched C
1
-C
8
alkyl or di(linear or branched C
1
-C
8
alkyl)amino; —(CH
2
)
q
—NR
4
—(CH
2
)
q
— wherein R
4
is hydrogen or C
1
-C
4
alkyl and q is 1, 2, 3or 4; or
a 1,2-cyclohexylene radical of formula:
 or a 1,2-aryl radical of formula
 wherein R
9
is hydrogen, SO
3
H, CH
2
OH or CH
2
NH
2
,
R and R
1
are each independently of the other nitro, NR
6
R
7
wherein R
6
is hydrogen or linear or branched C
1
-C
12
alkyl and R
7
is linear or branched C
1
-C
12
alkyl, with the proviso that R
6
and R
7
in the groups NR
6
R
7
are not identical, or —CH
2
—N
⊕
R
4
R
6
R
7
or —N
⊕
R
4
R
6
R
7
wherein R
4
, R
6
and R
7
are as defined above,
R
2
and R
3
are each independently of the other hydrogen, linear or branched C
1
-C
4
alkyl, unsubstituted aryl, or aryl substituted by cyano; by halogen; by OR
5
or COOR
5
wherein R
5
is hydrogen or linear or branched C
1
-C
4
alkyl; by nitro; by linear or branched C
1
-C
8
alkyl; by NHR
6
or NR
6
R
7
wherein R
6
and R
7
are identical or different and are each linear or branched C
1
-C
12
alkyl; by linear or branched C
1
-C
8
alkyl-R
8
wherein R
8
is a radical OR
5
, COOR
5
or NR
6
R
7
as defined above or is NH
2
; or by —N
⊕
R
4
R
6
R
7
wherein R
4
, R
6
and R
7
are as defined above,
and, when n and m are each 1, R
2
and R
3
are each hydrogen and Y is unsubstituted 1,2-cyclohexylene, R and R
1
are not each nitro in the 5- and 5′-position, respectively, and, when n and m are each 1, R
2
and R
3
are each hydrogen and Y is unsubstituted 1,2-ethylene, R and R
1
are not each N
⊕
(CH
3
)(C
2
H
5
)
2
in the 4- and 4′-position, respectively.
In compounds of formula (1) in which n is 2, the radicals R may have identical or different meanings. The same applies to compounds of formula (1) in which m is 2 in respect of the radicals R
1
.
When Y is a 1,2-cyclohexylene radical, that radical may be in either of its stereoisomeric cis/trans forms.
Preferably, Y is a cyclohexylene radical, a radical of formula (CH
2
)
r
— wherein r is an integer of from 1 to 8, or a radical of formula —C(R
5
)
2
—(CH
2
)
p
—C(R
5
)
2
— wherein p is an integer of from 0 to 6 and R
5
is hydrogen or C
1
-C
4
alkyl.
In especially preferred compounds of formula (1), Y is a cyclohexylene radical, a radical of formula —(CH
2
)
r
— wherein r is an integer of from 1 to 4, or a radical of formula —(CR
5
)
2
—(CR
5
)
2
— wherein the R
5
radicals are each independently of the others hydrogen or methyl.
Halogen is preferably chlorine, bromine or fluorine, chlorine being especially preferred.
When n or m is 1, the groups R and R
1
are preferably in the 4- or 5-position of the respective benzene ring.
When R
6
or R
7
is an alkyl radical, the alkyl group may be straight-chain or branched. Preferably, the alkyl group contains from 1 to 8, especially from 1 to 4, and more especially from 1 to 3, carbon atoms.
Preferably, the radicals R and R
1
are each nitro, NR
6
R
7
wherein R
6
and R
7
are each C
1
-C
4
alkyl, with the proviso that R
6
and R
7
are not identical, or —N
⊕
R
4
R
6
R
7
wherein R
4
, R
6
and R
7
are each C
1
-C
4
alkyl.
The radicals R
2
and R
3
are especially hydrogen, methyl, ethyl, or unsubstituted phenyl.
Aryl is, for example, naphthyl or, especially, phenyl.
Suitable anions include, for example, halide, for example chloride, bromide or iodide, perchlorate, sulfate, nitrate, hydroxide, BF
4
−
, PF
6
−
, carboxylate, acetate, tosylate and triflate. Of those, preference is given to chloride, bromide, iodide and acetate.
The compounds of formula (1) are prepared, for example, in a manner known per se from the corresponding ligands and a manganese compound. Preparation processes of that kind are described, for example, in U.S. Pat. Nos. 5,281,578 and 4,066,459.
The ligands of formula
wherein R, R
1
, R
2
, R
3
, Y, n and m are as defined for formula (1) are likewise novel. They are prepared in a manner known per se, for example by reacting a diamine of formula H
2
N—Y—NH
2
first of all with an aldehyde or ketone of formula
and then with an aldehyde or ketone of formula
In formulae (3) and (4), R, R
1
, R
2
, R
3
, n and m are as defined for formula (1). When, in the compounds of formula (2), (R)
n
has the same meaning as (R
1
)
m
and R
2
has the same meaning as R
3
then, for the synthesis of compounds of formula (2), one mol of a diamine of formula H
2
N—Y—NH
2
is reacted with two mols of an aldehyde or ketone of formula (3).
The diamines of formula H
2
N—Y—NH
2
and the aldehydes or ketones of formula (3) and (4) are known or can be prepared in a manner known per se.
The compounds of formula (1) are used as catalysts for oxidations using peroxy compounds, for example for bleaching textile material, without causing appreciable damage to fibres and colours.
The present invention accordingly further relates to a washing and cleaning process which comprises adding to the liquor, which comprises a peroxide-containing washing and cleaning agent, from 0.1 to 200 &mgr;mol of one or more compounds of formula (1) per liter of washing liquor.
The present invention relates also to a method of inhibiting the redeposition of migrating dyes present in a washing liquor, which comprises adding to the washing liquor, which comprises a peroxide-containing washing agent, from 0.5 to 150 mg, preferably from 1.5 to 75 mg, especially from 7.5 to 40 mg, of one or more compounds of formula (1) per liter of washing liquor.
The present invention relates furthermore to a washing agent containing
I) from 5 to 90%, preferably from 5 to 70%, A) of an anionic surfactant and/or B) of a non-ionic surfactant,
II) from 5 to 70%, preferably from 5 to 50%, especially from 5 to 40%, C) of a builder substan

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