Metal complexes of tripodal ligands

Details Metal complexes of tripodal ligands Metal complexes of tripodal ligands

2002-01-10

2004-10-05

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

C510S174000, C510S194000, C510S220000, C564S274000, C564S275000

Reexamination Certificate

active

06800775

ABSTRACT:

The present invention relates to the use of metal complexes of tripodal ligands based on tris(2-aminoethyl)amine as catalysts which enhance the action of peroxygen compounds in washing, cleaning and disinfecting processes. The invention further relates to compositions of the metal complexes and peroxygen compounds used in such processes and to the novel metal complexes and ligands and also to processes for preparing them.
It is known that some manganese complexes, especially those of the salene type, are useful catalysts for oxidations with peroxygen compounds, especially as part of a washing processes. It is also known that certain other manganese complexes have a marked bleaching effect on dirt and dyes in wash liquors. There is nevertheless a demand for further compounds having an improved effect and/or having a broader application range, subject to the proviso that no significant fibre and dye damage may occur when applied to textile material.
It has now been found that certain metal complexes of tripodal ligands obtainable by reacting tris(2-aminoethyl)amine with aldehydes or ketones substantially meet the stated requirements when used as catalysts in that they enhance the action of peroxygen compounds in a wide variety of applications to a higher degree without occurrence of fibre and dye damage. Surprisingly, the enhanced effect occurs in applications including the following on using the metal complexes of such ligands in aqueous solution together with peroxygen compounds:
a) bleaching spots or stains on textile material as part of a washing process,
b) preventing the redepositon of migrating dyes during the washing of textile material,
c) cleaning hard surfaces, especially crockery or glass,
d) cleaning hard surfaces, especially tiles, particularly to remove mold stains,
e) using washing and cleaning solutions having an antibacterial effect, and
f) removing printing inks from printed wastepaper (de-inking).
The invention accordingly provides for the use of metal complexes containing a tripodal ligand of the formula
where
R
1
, R
2
, R
3
, R
4
, R
1
′, R
2
′, R
3
′, R
4
′, R
1
″, R
2
″, R
3
″ and R
4
″ are each independently hydrogen, cyano, halogen, SO
3
M, where M is hydrogen, an alkali metal cation, an alkaline earth metal cation, ammonium or an organic ammonium cation, SO
2
NH
2
, SO
2
NHR
5
, SO
2
N(R
5
)
2
, OR
5
or COOR
5
, where R
5
is hydrogen or linear or branched C
1
-C
4
alkyl, nitro, linear or branched C
1
-C
8
alkyl, linear or branched fluorinated or perfluorinated C
1
-C
8
alkyl, NHR
6
, R
6
NR
7
, N⊕R
6
R
7
R
10
or linear or branched C
1
-C
8
alkyl-R
8
, where R
8
is OR
5
, COOR
5
, NH
2
, NHR
6
, NR
6
R
7
or N⊕R
6
R
7
R
10
, where R
6
, R
7
and R
10
are identical or different and each is linear or branched C
1
-C
12
alkyl or where R
6
and R
7
combine with the joining nitrogen atom to form a 5-, 6- or 7-membered ring, which may contain further heteroatoms, and where R
9
, R
9
′ and R
9
″ are each independently hydrogen, linear or branched C
1
-C
8
alkyl or aryl, as catalysts for oxidations with peroxygen compounds.
Particular preference is given to the use of Mn(III) and Fe(III) complexes containing a ligand of the above formula (1), especially an Mn(III) and Fe(III) complex which contains a ligand of the above formula (1) and metal in a molar ratio of 1:1.
Halogen is preferably chlorine, bromine or fluorine, particularly preferably chlorine.
Alkyl is particularly alkyl having 1 to 4 carbon atoms, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R
6
and R
7
combining with the joining nitrogen atom to form a 5-, 6- or 7-ring are in particular a pyrrolidine, piperidine, morpholine or piperazine ring. The piperazine ring may be substituted, for example by alkyl, on the nitrogen atom not attached to the phenyl or alkyl radical.
Aryl is for example naphthyl or particularly phenyl.
R
9
, R
9
′ and R
9
″ are each preferably independently hydrogen or C
1
-C
4
alkyl, especially hydrogen.
An alkali cation M in the SO
3
M radicals may be for example lithium, potassium or particularly sodium, an alkaline earth metal cation M is selected in particular from magnesium and calcium.
Very particular preference is given to the use of the 1:1 Me(III) complexes of the formula
where Me is Mn or Fe, R
1
, R
1
′ and R
1
′ are each independently hydrogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, hydroxyl, nitro, NHR
6
, NR
6
R
7
or -N⊕R
5
R
6
R
7
, where R
5
, R
6
and R
7
are each independently C
1
-C
4
alkyl, as catalysts for oxidations with peroxygen compounds.
Me in the formula (2) is preferably manganese.
The metal complexes containing a tripodal ligand of the formula (1) are preferably used in aqueous solution together with peroxygen compounds for bleaching spots or stains on textile material or for preventing the redeposition of migrating dyes as part of a washing process, or for cleaning hard surfaces, especially crockery or glass.
The ligands of the formula (1) are also useful in the uncomplexed form, as catalysts in aqueous solution with peroxygen compounds for bleaching spots or stains on textile material.
Preference for this use is given to the ligands of the formula
where
R
1
, R
1
′ and R
1
″ are each independently hydrogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, hydroxyl, nitro, NHR
6
, NR
6
R
7
or N⊕R
5
R
6
R
7
, where R
5
, R
6
and R
7
are each independently C
1
-C
4
alkyl and R
2
, R
2
′ and R
2
″ are each independently hydrogen, linear or branched C
1
-C
8
alkyl or aryl.
Individual metal complexes containing a tripodal ligand of the formula (1) are already known, for example from S. Chandra, P. Chakraborty, A. Charkaravorty, J. Chem. Soc., Dalton Trans. (1993), 6,863. Novel metal complexes are the manganese(III) and iron(III) complexes containing a tripodal ligand of the formula
where R
1
, R
2
, R
3
, R
4
, R
1
′, R
2
′, R
3
′, R
4
′, R
1
″, R
2
″, R
3
″ and R
4
″ are each independently hydrogen, cyano, halogen, SO
3
M, where M is hydrogen, sodium, calcium, magnesium, ammonium or an organic ammonium cation, SO
2
NH
2
, SO
2
NHR
5
, SO
2
N(R
5
)
2.
, OR
5
or COOR
5
, where R
5
is hydrogen or linear or branched C
1
-C
4
alkyl, nitro, linear or branched C
1
-C
8
alkyl, linear or branched fluorinated or perfluorinated C
1
-C
8
alkyl, NHR
6,
NR
6
R
7,
NR⊕R
6
R
7
R
10
or linear or branched C
1
-C
8
alkyl-R
8
, where R
8
is OR
5
, COOR
5
, NH
2
, NHR
6
, NR
6
R
7
or N⊕R
6
R
7
R
10
, where R
6
, R
7
and R
10
are identical or different and each is linear or branched C
1
-C
12
alkyl or where R
6
and R
7
combine with the joining nitrogen atom to form a 5-, 6- or 7-membered ring, which may contain further heteroatoms, and where R
9
, R
9
′ and R
9
″ are each independently hydrogen, linear or branched C
1
-C
8
alkyl or aryl, subject to the condition that in the manganese(III) complex at least one of the substituents R
1
, R
2
, R
3
, R
4
, R
1
′, R
2
′, R
3
′, R
4
′, R
1
″, R
2
″, R
3
″, R
4
″, R
9
, R
9
′ and R
9
″ has a meaning other than hydrogen and that at least one of the substituents R
3
, R
3
′ and R
3
″ has a meaning other than chlorine when the substituents R
1
, R
2
, R
4
, R
1
′, R
2
′, R
4
′, R
1
″, R
2
″, R
4
″, R
9
, R
9
′ and R
9
″ are all hydrogen.
These manganese(III) and iron(III) complexes also form part of the subject-matter of the present invention. They are obtained in a conventional manner by reacting a ligand of the formula (1) with a manganese or iron compound to form the corresponding metal complex. Such methods of operation are described for example in U.S. Pat. No. 5,281,578 and No. 4,066,459. Also new are the ligands of the formula
where
R
1
, R
2
, R
3
, R
4
, R
1
′, R
2
′, R
3
′, R
4
′, R
1
″, R
2
″, R
3
″ and R
4
″

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