Process for the preparation of manganese complexes of salen...

Details Process for the preparation of manganese complexes of salen... Process for the preparation of manganese complexes of salen...

2003-01-02

2004-09-21

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

Reexamination Certificate

active

06794526

ABSTRACT:

The present invention relates to a process for the preparation of manganese complexes of salen compounds, to the compounds prepared according to that process, and to the use thereof in washing and cleaning solutions.
Manganese complexes of salen compounds are known, for example, from EP-A-902 083 and EP-A-955 289. They are usually prepared from the appropriate salen ligands by reaction with a manganese salt in ethanolic solution in the presence of air as oxidizing agent. The ligands themselves are obtained, for example, by reacting the appropriate di- or tri-amines with the appropriate o-hydroxyaldehydes in methanolic or ethanolic solution and crystallising out the ligands. Since, however, on an industrial scale working in methanol or ethanol at elevated temperature in the presence of air necessitates complex safety measures, the need existed for an improved method of synthesis.
It has now been found, surprisingly, that the reaction of the ligand with the manganese salt can advantageously be carried out in dimethylformamide (DMF) as solvent, and at the same time it is possible to operate at a temperature sufficiently far below the flash point of the solvent that even in the presence of air there are no safety problems. The preparation of the ligand can be carried out, for example, in water or, preferably, likewise in DMF. Surprisingly, it is even possible to carry out the synthesis of the ligand and the preparation of the manganese complex in DMF as a “one-pot reaction”, that is to say without isolation and purification of the ligand.
The present invention accordingly relates to a process for the preparation of manganese complexes of salen compounds of formula
in which formulae
A is an anion;
n, m and p are each independently of the others 0, 1, 2 or 3,
R, R
1
and R
1
′ are each independently of the others cyano; halogen; OR
4
or COOR
4
, wherein R
4
is hydrogen or linear or branched C
1
-C
4
alkyl; nitro; linear or branched C
1
-C
8
alkyl; linear or branched partially fluorinated or perfluorinated C
1
-C
8
alkyl; NR
5
R
6
, wherein R
5
and R
6
are identical or different and are each independently of the other hydrogen or linear or branched C
1
-C
12
alkyl; or linear or branched C
1
-C
8
alkyl-R
7
, wherein R
7
is a radical NH
2
, OR
4
, COOR
4
or NR
5
R
6
as defined above; or —CH
2
—N
⊕
R
4
R
6
R
7
or —N
⊕
R
4
R
5
R
6
, wherein R
4
, R
5
and R
6
are as defined above,
R
2
and R
3
are each independently of the other hydrogen, linear or branched C
1
-C
4
alkyl or unsubstituted aryl or aryl that is substituted by cyano; by halogen; by OR
4
or COOR
4
, wherein R
4
is hydrogen or linear or branched C
1
-C
4
alkyl; by nitro; by linear or branched C
1
-C
8
alkyl; by NHR
5
or NR
5
R
6
, wherein R
5
and R
6
are identical or different and are each hydrogen or linear or branched C
1
-C
12
alkyl or wherein R
5
and R
6
together with the nitrogen atom linking them form a 5-, 6- or 7-membered ring that may contain further hetero atoms; or by linear or branched C
1
-C
8
alkyl-R
7
, wherein R
7
is a radical NH
2
, OR
4
, COOR
4
or NR
5
R
6
as defined above; or by —N
⊕
R
4
R
5
R
6
, wherein R
4
, R
5
and R
6
are as defined above,
R
8
radicals are each independently of the others hydrogen or linear or branched C
1
-C
4
alkyl,
Y is a linear or branched alkylene radical of formula —[C(R
4
)
2
]
r
—, wherein r is an integer from 1 to 8 and the R
4
radicals are each independently of any other(s) as defined above; —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 as defined above and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene radical of formula:
wherein R
9
is hydrogen, SO
3
H, CH
2
OH or CH
2
NH
2
,
wherein in formula (1) the phenyl rings may together carry no more than three tert-butyl substituents, and wherein, when Y is 2-hydroxypropylene and m and n are each 0, R
2
and R
3
may not both be H, and wherein when Y is ethylene or o-phenylene and m and n are each 0 and MnO is used as the manganese compound, R
2
and R
3
may not both be H,
which process comprises reacting a ligand of formula
wherein R, R
1
, R
1
′, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, Y, A, n, m and p are as defined for formulae (1), (2) and (3),
with a manganese compound in dimethylformamide as solvent.
In the compounds of formula (1) or (3) in which n, m or p is 2 or 3, the radicals R, R
1
and R
1
′ have identical or different meanings. The same applies to compounds of formula (2) in respect of the R
8
radicals.
When Y is a 1,2-cyclohexylene radical, that radical may be in either of its stereoisomeric cis/trans forms.
Preferably, Y is a radical of formula —(CH
2
)
r
— wherein r is an integer from 1 to 8, or a radical of formula —C(R
5
)
2
—(CH
2
)
p
—C(R
5
)
2
— wherein p is a number from 0 to 6 and R
5
is hydrogen or C
1
-C
4
alkyl.
In especially preferred compounds of formulae (1) and (2), Y is a radical of formula —(CH
2
)
r
— wherein r is an integer 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 R, R
1
or R
1
′ is di(C
1
-C
12
alkyl)amino, the alkyl group may be straight-chain or branched. Preferably it contains from 1 to 8, especially from 1 to 4, and more especially 1 or 2, carbon atoms.
Preferably, the radicals R, R
1
and R
1
′ are hydrogen, nitro, OR
4
, COOR
4
or N(R
4
)
2
, wherein R
4
is hydrogen or C
1
-C
4
alkyl, especially methyl or ethyl.
The radicals R
2
and R
3
are especially hydrogen, methyl, ethyl or unsubstituted phenyl.
Aryl is, for example, naphthyl or especially phenyl.
When R
5
and R
6
together with the nitrogen atom linking them is a 5-, 6- or 7-membered ring, that ring is especially a pyrrolidine, piperidine, morpholine or piperazine ring. The piperazine ring may be substituted, for example by alkyl, at the nitrogen atom that is not bonded to the phenyl radical.
Suitable anions include, for example, halide, for example chloride, perchlorate, sulfate, nitrate, hydroxide, BF
4
−
, PF
6
−
, carboxylate, acetate, tosylate and triflate. Of those, preference is given to chloride, acetate and carboxylate.
The ligands of formulae (4), (5) and (6) are known or can be prepared in a manner known per se.
In the process according to the invention, the reaction of those ligands with a manganese compound is carried out in DMF at a temperature of from approximately 10° C. to the boiling point of DMF, but preferably at a temperature of from 20 to 70° C., especially from 20 to 40° C.
The manganese compounds used are especially manganese(II) salts, especially manganese(II) chloride, sulfate or acetate.
Preferably, the manganese compound is added in slight excess, especially an excess of from 0.5 to 3%.
During the reaction, preferably air, as oxidizing agent, is passed through the reaction mixture, but it is also possible to use other oxidizing agents.
After the reaction, the manganese complex is isolated in a manner known per se, for example by crystallising it out by the addition of sodium chloride and then distilling off the DMF at elevated temperature in vacuo, suspending the residue in water and filtering.
In an especially preferred embodiment of the process according to the invention, the ligands used have not been formed and isolated beforehand but instead the synthesis of the ligand and the reaction to form the manganese complex are carried out in DMF as a so-called one-pot reaction.
The present invention accordingly relates also to a process for the preparation of manganese complexes of the above formulae (1), (2) and (3) which comprises, in DMF as solvent, reacting a diamine of formula
H
2
N—Y—NH
2
  (7)
with an o-hydroxybenzaldehyde of formula
or reacting the compound of formula
N(—CH
2
—CH
2
—NH
2
)
3
  (10)
with an o-hydroxybenzaldehyde of formula (8), in which formulae R,

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