Method for producing 3,7-diaza-bicyclo[3.3.1]nonane-metal complex solutions
The invention relates to a method for producing homogeneous solutions of metal complexes of general formula (2): [M a L x X n ]Y m , where M is a metal from the group comprising Mn(II), Mn(III), Mn(IV), Fe(III), Fe(III) or Fe(IV), X is a coordinated compound selected from mono- bi- or tri-charged anions or neutral molecules which are able to coordinate with a metal mono- bi- or tri-dentate, Y is a non-coordinated counter-ion which ensures charge equalization of the complex, L is a ligand of general formula (1) or the protonized or de-protonized form thereof, and a, x, n, m, R, R 1 , R 2 , R 3 and z are as specified in claim 1 , in diols or polyols, the monoethers or mixtures of said substances. Said method is characterized in that a ligand of the formula (1) is reacted with an iron or manganese salt in a heterogeneous reaction in the diol or polyol, the monoethers or mixtures of these substances.
1. A process for preparing a homogeneous solution comprising at least one metal complex of formula (2)
[M a L x X n ]Y m (2)
where
M is a metal selected from the group consisting of Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III) and Fe(IV),
X is a coordinating compound selected from the group consisting of singly, doubly and triply charged anions or uncharged molecules capable of mono-, bi- or tridentate coordination to a metal,
Y is a noncoordinating counterion which ensures the charge balance of the complex,
a is a number from 1 to 2,
x is a number from 1 to 2,
n is a number from 0 to 4,
m is a number from 0 to 8, and
L is a ligand of formula (1) or the protonated or deprotonated form thereof
where
R is hydrogen, hydroxyl or C 1 -C 4 alkyl;
R 1 is C 1 -C 4 alkyl, C 6 -C 10 aryl, pyridinyl-C 1 -C 4 -alkyl or (CH 2 ) k N(C 1 -C 4 alkyl) 2 ;
R 2 is C 1 -C 20 alkyl, C 6 -C 10 aryl or pyridinyl-C 1 -C 4 -alkyl;
R 3 is C 1 -C 4 alkyl;
z is C═O or C(OH) 2 and
k is a number from 1 to 6,
in di- or polyols, monoethers thereof or mixtures of these substances, which comprises the step of reacting at least one ligand of the formula (1) with an iron or manganese salt in heterogeneous reaction in the di- or polyol, the monoethers or mixtures of these substances to produce the homogeneous solution comprising at least one metal complex of formula (2).
2. The process as claimed in claim 1 , wherein X is selected from the group consisting of OH − , NO 3 − , NO, S 2− , R a S − , PO 4 3− , H 2 O, CO 3 2− , R b OH, Cl − , Br − , CN − , ClO 4 − , R a COO − and SO 4 2− , where R a is H or C 1 -C 4 alkyl and R b is C 1 -C 4 alkyl.
3. The process as claimed in claim 1 , wherein Y is selected from the group consisting of R c SO 4 − , SO 4 2− , NO 3 − , Cl − , Br, I − , ClO 4 − , BF 4 − , PF 6 − and R c SO 3 − , where R c is H or C 1 -C 4 alkyl.
4. The process as claimed in claim 1 , wherein the solutions comprising at least one complex of the formula [FeLCl]Cl, [FeL(SO 4 )], [MnLCl]Cl or [MnL(SO 4 )] are prepared, where L is selected from the group consisting of dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py3o), dimethyl 2,4-di(2-pyridyl)3-(pyridin-2-ylmethyl)-7-methyl-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py3u), diethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate, dimethyl 2,4-di(2-pyridyl)-3,7-bis(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py4), dimethyl 2,4-di(2-pyridyl)-3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py2), diethyl 2,4-di(2-pyridyl)-3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate, dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(N,N′-dimethylethylamine)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate and the corresponding dihydroxy ketals.
5. The process as claimed in claim 1 , wherein the di- or polyols have 2 to 6 carbon atoms and 2 to 4 OH groups and the monoethers of these di- and polyols contain alcohol units originating from monoalcohols having 1 to 4 carbon atoms.
6. The process as claimed in claim 1 , wherein the process is conducted in the di- or polyols or mixtures thereof.
7. The process as claimed in claim 5 , wherein the process is conducted in 1,2-propylene glycol.
8. The process as claimed in claim 1 , wherein the solution prepared contains 0.01 to 30% by weight of complex of the formula (2).
9. The process as claimed in claim 1 , wherein the complexation reaction is performed within the temperature range from 5 to 80° C.
10. The process as claimed in claim 1 , wherein the ligands of the formula (1) are selected from the group consisting of dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py3o), dimethyl 2,4-di(2-pyridyl)-3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py2) and the corresponding dihydroxy ketals.
11. The process as claimed in claim 1 , wherein the complexation reaction is performed by first introducing the ligand of the formula (1) into the di- or polyol, monoethers thereof or mixtures of these substances to prepare a suspension containing 0.5 to 60% by weight of ligand and then adding the metal salt in solid or dissolved form within the temperature range from 5 to 80° C.
12. The process as claimed in claim 1 , wherein the iron or manganese salt used is iron(II) chloride, iron(II) sulfate, manganese(II) chloride or manganese(II) sulfate.
13. The process as claimed in claim 1 , wherein z is C(OH) 2 and the metal salts are metal salt hydrates.
14. The process as claimed in claim 13 , wherein the iron or manganese salt hydrates are selected from the group consisting of Fe(II)Cl 2 .4H 2 O and Mn(II)Cl 2 .4H 2 O.
15. The process as claimed in claim 1 , wherein the solution comprising at least one complex of the formula [MnLCl]Cl or [FeLCl]Cl in 1,2-propylene glycol is prepared, where L is dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py3o), dimethyl 2,4-di(2-pyridyl)-3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py2), or the corresponding dihydroxy ketals (z=C(OH) 2 ), and dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate, 2,4-di(2-pyridyl)-3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate or the corresponding dihydroxy ketals or mixtures of these substances are reacted with manganese(II) chloride or iron(II) chloride in 1,2-propylene glycol.
16. The process as claimed in claim 1 , wherein the at least one ligand L is in the form of a ketone.
17. The process as claimed in claim 1 , wherein the solution prepared contains 0.1 to 15% by weight of complex of the formula (2).
18. The process as claimed in claim 1 , wherein the solution prepared contains 0.5 to 8% by weight of complex of the formula (2).
19. The process as claimed in claim 1 , wherein the complexation reaction is performed within the temperature range from 10 to 70° C.
20. The process as claimed in claim 1 , wherein the complexation reaction is performed within the temperature range from 15 to 55° C.