EP0000487A1 - Compounds containing enol groups, metal chelates made therefrom, their preparation and use as light stabilizers, especially for polymeric substances. - Google Patents

Abstract

The compounds of the general formula I M <q⊕> [L <⊖>] q / r. mA (I), where M <q⊕> is a double or triple positively charged metal ion, and q is 2 or 3, and r is 1 or 2, the quotient q / r being 1,1,5,2 or 3, and L is a piperidine which is substituted by at least one enolate group in the 1- or 4-position and whose ring nitrogen is sterically hindered at the adjacent positions by alkyl substituents, and m is 0, 1 or 2, and A is H2O or an amine. are valuable light stabilizers especially for high molecular weight compounds.

Description

The present invention relates to new compounds containing enol groups, their metal chelates, their preparation and use as light stabilizers in organic material, and the organic material protected with the aid thereof.

DT-OS 2,625,967 describes metal complexes with sterically hindered amines and simply charged anions as stabilizers for synthetic polymers.

New compounds containing enol groups and their chelate complexes with double and triple-charged metal cations have now been found, which are notable for good sun protection and good extraction stability and have good compatibility in polymers.

worin

• M^q⊕ ein zweifach oder dreifach positiv geladenes Metallion ist, und
• q 2 oder 3 ist, und
• r 1 oder 2 ist, wobei der Quotient q/r 1, 1.5, 2 oder 3 ist, und
• L ein durch mindestens eine Enolatgruppe in 1-oder 4-Stellung substituierter Piperidin, dessen RingStickstoff durch Alkylsubstituenten an den benachbarten Stellungen sterisch gehindert ist, bedeutet, und
• m 0, 1 oder 2 ist, und
• A H₂O oder ein Amin ist.

The new compounds correspond to the general formula I.

wherein

• M ^{q⊕ is} a double or triple positively charged metal ion, and
• q is 2 or 3, and
• r is 1 or 2, the quotient q / r being 1, 1.5, 2 or 3, and
• L is a piperidine which is substituted by at least one enolate group in the 1- or 4-position and whose ring nitrogen is sterically hindered at the adjacent positions by alkyl substituents, and
• m is 0, 1 or 2, and
• AH ₂ O or an amine.

• M^q⊕ ein zweifach oder dreifach positiv geladenes Metallion ist, und
• q 2 oder 3 ist, und
• r 1, oder 2 ist, wobei der Quotient q/r 1, 1.5, 2 oder 3 bedeutet, und
• L eine Gruppe der Formel II
  
  ist, worin
• R₁ Wasserstoff oder C₁-C₄Alkyl ist, und
• Z₁ Wasserstoff, C₁-C₁₂ Alkyl, _C3-_C8 Alkenyl, ^C ₃-^C ₄ Alkinyl, C₂-C₂₁ Alkoxyalkyl, C₇-C₈ Aralkyl, eine aliphatische Acylgruppe mit 1-4 C-Atomen, oder eine der Gruppen -CH₂COOR₂ oder -CH₂-CH(R₃)-OR₄, oder einen Rest -(CH₂)₄-R₅, -CH₂-CH=CH-CH₂-R₅,
  
  oder eine Gruppe der Formel III
  
  bedeutet, wobei
• ^R ₂ C₁-C₈Alkyl, C₃-C₆ Alkenyl, Phenyl, C₇-C₈ Aralkyl oder Cyclohexyl ist, und
• R₃ Wasserstoff, Methyl oder Phenyl ist, und
• R₄ eine aliphatische C₁-C₁₈ Acylgruppe, eine aromatische C₇ Acylgruppe, eine araliphatische C₈-C₉ Acylgruppe oder eine alicyclische C₆-C₉ Acylgruppe bedeutet, wobei der aromatische Teil gegebenenfalls mit Chlor, C₁-C₄ Alkyl, C₁-C₈Alkoxy, und/oder Hydroxy substituiert sein kann bedeutet, und
• R₅ eine Gruppe der Formel IV
  
  bedeutet, worin R₁, Z₂ und Z₃ die hier angegebene Bedeutung haben, und
• R₆ eine Gruppe der Formel V
  
  ist, worin
• R₉ Wasserstoff oder C₁-C₄Alkyl ist, und
• R₇ und R₈ unabhängig voneinander Wasserstoff, Methyl, Phenyl, C₂-C₉ Alkoxymethyl oder ein Rest -CH₂O-R₆ ist, worin R₆ die oben definierte Bedeutung hat, und
• a 0, 1 oder 2, und
• b 0 oder 1 ist, und
• c 0 oder, falls a und/oder b von 0 verschieden sind, auch 1 ist, und
• X und Y unabhängig voneinander -0- oder -NR₁₀, worin
• R₁₀ Wasserstoff, C₁-C₁₂ Alkyl, C₃-C₈ Alkenyl, Cyclohexyl, C₃-C₂₁ Alkoxyalkyl, C₇-C₁₃ Aralkyl, gegebenenfalls durch C₁-C₈ Alkyl und/oder C₁-C₈ Alkoxy substituiertes Phenyl oder eine Gruppe -CH₂-CH₂-O-R₆, worin R₆ die oben angegebene _Be-deutung hat, ist, und R₁₀ ferner eine Gruppe der Formel VI
  
  worin
• R₁ die oben angegebene Bedeutung hat, und
• R11 Wasserstoff, C₁-C₁₂ Alkyl, C₃-C₈ Alkenyl, C₂-C₂₁ Alkoxyalkyl, C₇-C₈ Aralkyl, eine aliphatische Acylgruppe mit 1-4 C-Atomen oder eine Gruppe -CH₂COOR₂, worin R₂ die oben definierte Bedeutung hat, bedeutet, und
• Z₂ Wasserstoff, C₂-C₁₈ aliphatisches Acyloxy, gegebenenfalls durch C₁-C₈ Alkyl oder C₁-C₈ Alkoxy substituiertes Benzoyloxy oder eine gegebenenfalls C₁-C₈ N-alkyl-substituierte C₂-C₁₈ Acylamidogruppe ist, oder eine der Gruppen -R₁₂,
  
  oder
  
  ist, worin d 2 bis 10 ist und R₁₂ eine Gruppe der Formel VII
  
  ist, worin .
• R₁ und Z₁ die oben angegebene Bedeutung haben, oder
• Z2 ferner eine Gruppe der Formel VIII
  
  darstellt, worin
• R₁₂ die oben angegebene Bedeutung hat und
• X' -0- oder -N-R₁₄ ist, wobei
• R₁₄ Wasserstoff oder C₁-C₄ Alkyl bedeutet, und
• R₁₃ -(CH₂)_e- oder eine Gruppe
  
  ist, wobei e 0 bis 8 ist, und
• R₁₅ und R₁₆ unabhängig voneinander Wasserstoff, C₁-C₁₂ Alkyl, C₃-C₈ Alkenyl, C₇-C₁₁ Aralkyl, Cyanomethyl, Cyanoäthyl oder eine Gruppe -CH₂COOR₁₇, wobei
• R₁₇ Methyl oder Aethyl ist, bedeuten, oder
• Z₂ eine der Gruppen
  
  
  oder
  
  bedeutet worin
• R₆, R₇ und R₁₂ die oben angegebene Bedeutung haben, und
• R₁₈ Wasserstoff, C₁-C₈ Alkyl, Allyl, Phenyl oder Benzyl ist, und
• R₁₉ Wasserstoff, C₁-C₈ Alkyl, Allyl oder Benzyl ist, und
• R₂₀ C₁-C₄ Alkyl oder eine Gruppe der Formel V mit oben angegebener Bedeutung ist und
• R₂₁ C₂-C₆ Alkylen, Cyclohexyliden, Phenylen, Diphenylen, 4,4'-Diphenylenoxyd oder 4,4'-Diphenylenmethan ist, oder
• Z₂ ferner eine Gruppe der Formeln XII, XIII oder XIV
  
  
  ist, worin a, b, c, X, Y, R₆, R₇ und R₈ die oben angegebene Bedeutung haben, und
• f,a' und b' 0 oder 1 sind, und .
• g 0 oder falls a' und/oder b' von 0 verschieden sind, auch 1 ist, und
• R₂₂ und R₂₃ unabhängig voneinander Wasserstoff, C₁-C₄ Alkyl, . Cyclohexyl, Phenyl, Benzyl, α-Methylbenzyl oder α,α-Dimethylbenzyl bedeuten, und
• Z₃ Wasserstoff oder Cyano ist, oder
• Z₂ und Z₃ zusammen eine der Gruppen XV, XVI oder XVII
  
  
  oder
  
  bedeuten, worin
• R₆ oben angegebene Bedeutung hat, und
• R₂₄ Wasserstoff, Methyl oder Aethyl ist, und
• R₂₅ Wasserstoff, C₁-C₁₈ Alkyl, C₃-C₈ Alkenyl, Cyclohexyl, C₇-C₈ Aralkyl oder eine Gruppe -CH₂-C^OOR₂₆ oder -CH₂-CH(R₈)-O-R₆, bedeutet, wobei
• R₂₆ C₁-C₁₈ Alkyl ist, und R₆ und R₈ die oben angegebene Bedeutung haben, und
• m 0, 1 oder 2 ist, und
• A H₂0 oder ein Amin der Formel (XVIII)
  
  ist, worin
• R₂₇ gegebenenfalls substituiertes Alkyl, Cycloalkyl, Aryl, Aralkyl, eine gegebenenfalls substituierte Aminoalkylgruppe oder eine Piperidinylgruppe ist, und
• R₂₈ Wasserstoff oder gegebenenfalls substituiertes Alkyl, Cycloalkyl, eine gegebenenfalls substituierte Aminoalkylgruppe oder eine gegebenenfalls substituierte Piperidinylgruppe bedeutet, oder
• R₂₇ und R₂₈ zusammen mit dem N-Atom einen durch Alkylgruppen . substituierten oder unsubstituierten Pyrrolidin-, Piperidin- oder Morpholinring bilden, und
• R₂₉ Wasserstoff oder gegebenenfalls substituiertes Alkyl bedeutet.

The present invention relates in particular to compounds of the formula I in which

• M ^{q⊕ is} a double or triple positively charged metal ion, and
• q is 2 or 3, and
• r is 1 or 2, the quotient q / r being 1, 1.5, 2 or 3, and
• L is a group of formula II
  
  is what
• R _{1 is} hydrogen or C ₁ -C ₄ alkyl, and
• Z _{1 is} hydrogen, C ₁ -C ₁₂ alkyl, _C3 - _C8 alkenyl, ^C ₃ - ^C ₄ alkynyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₈ aralkyl, an aliphatic acyl group with 1-4 C atoms, or one the groups -CH ₂ COOR ₂ or -CH ₂ -CH (R ₃ ) -OR ₄ , or a radical - (CH ₂ ) ₄ -R ₅ , -CH ₂ -CH = CH-CH ₂ -R ₅ ,
  
  or a group of formula III
  
  means where
• ^R _{2 is} C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl, and
• R _{3 is} hydrogen, methyl or phenyl, and
• R _{4 represents} an aliphatic C ₁ -C ₁₈ acyl group, an aromatic C ₇ acyl group, an araliphatic C ₈ -C ₉ acyl group or an alicyclic C ₆ -C ₉ acyl group, the aromatic part optionally containing chlorine, C ₁ -C ₄ alkyl , C ₁ -C ₈ alkoxy, and / or hydroxy may be substituted, and
• R _{5 is} a group of formula IV
  
  means, wherein R ₁ , Z ₂ and Z _{3 have} the meaning given here, and
• R _{6 is} a group of formula V.
  
  is what
• R _{9 is} hydrogen or C ₁ -C ₄ alkyl, and
• R ₇ and R _{8 are} independently hydrogen, methyl, phenyl, C ₂ -C ₉ alkoxymethyl or a radical -CH ₂ OR ₆ , in which R _{6 has} the meaning defined above, and
• a 0, 1 or 2, and
• b is 0 or 1, and
• c is 0 or, if a and / or b are different from 0, is also 1, and
• X and Y independently of one another -0- or -NR ₁₀ , wherein
• R _{10 is} hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₈ alkenyl, cyclohexyl, C ₃ -C ₂₁ alkoxyalkyl, C ₇ -C ₁₃ aralkyl, optionally by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ alkoxy-substituted phenyl or a group -CH ₂ -CH ₂ -OR ₆ wherein R ₆ has the above mentioned _B-e importance has is and R ₁₀ is furthermore a group of the formula VI
  
  wherein
• R _{1 has} the meaning given above, and
• R11 is hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₈ alkenyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₈ aralkyl, an aliphatic acyl group with 1-4 C atoms or a group -CH ₂ COOR ₂ , wherein R _{2 has} the meaning defined above, means, and
• Z _{2 is} hydrogen, C ₂ -C ₁₈ aliphatic acyloxy, optionally substituted by C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy benzoyloxy or an optionally C ₁ -C ₈ N-alkyl substituted C ₂ -C ₁₈ acylamido group, or one of the groups -R ₁₂ ,
  
  or
  
  is where d is 2 to 10 and R _{12 is} a group of formula VII
  
  is what.
• R ₁ and Z _{1 have} the meaning given above, or
• Z2 also a group of formula VIII
  
  represents what
• R _{12 has} the meaning given above and
• X 'is -0- or -NR ₁₄ , where
• R _{14 is} hydrogen or C ₁ -C ₄ alkyl, and
• R ₁₃ - (CH ₂ ) _e - or a group
  
  is, where e is 0 to 8, and
• R ₁₅ and R ₁₆ independently of one another hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₈ alkenyl, C ₇ -C ₁₁ aralkyl, cyanomethyl, cyanoethyl or a group -CH ₂ COOR ₁₇ , where
• R _{17 is} methyl or ethyl, or
• Z ₂ one of the groups
  
  
  or
  
  means in what
• R ₆ , R ₇ and R _{12 have} the meaning given above, and
• R _{18 is} hydrogen, C ₁ -C ₈ alkyl, allyl, phenyl or benzyl, and
• R _{19 is} hydrogen, C ₁ -C ₈ alkyl, allyl or benzyl, and
• R _{20 is} C ₁ -C ₄ alkyl or a group of formula V with the meaning given above and
• R _{21 is} C ₂ -C ₆ alkylene, cyclohexylidene, phenylene, diphenylene, 4,4'-diphenylene oxide or 4,4'-diphenylene methane, or
• Z ₂ also a group of the formulas XII, XIII or XIV
  
  
  is where a, b, c, X, Y, R ₆ , R ₇ and R _{8 have} the meaning given above, and
• f, a 'and b' are 0 or 1, and.
• g is 0 or, if a 'and / or b' are different from 0, is also 1, and
• R ₂₂ and R ₂₃ independently of one another hydrogen, C ₁ -C ₄ alkyl,. Cyclohexyl, phenyl, benzyl, α-methylbenzyl or α, α-dimethylbenzyl mean, and
• Z _{3 is} hydrogen or cyano, or
• Z ₂ and Z ₃ together one of the groups XV, XVI or XVII
  
  
  or
  
  mean what
• R ₆ has the meaning given above, and
• R _{24 is} hydrogen, methyl or ethyl, and
• R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, cyclohexyl, C ₇ -C ₈ aralkyl or a group -CH ₂ -C ^O OR ₂₆ or -CH ₂ -CH (R ₈ ) -OR ₆ , means, where
• R _{26 is} C ₁ -C ₁₈ alkyl, and R ₆ and R _{8 have} the meaning given above, and
• m is 0, 1 or 2, and
• AH ₂ 0 or an amine of the formula (XVIII)
  
  is what
• R _{27 is} optionally substituted alkyl, cycloalkyl, aryl, aralkyl, an optionally substituted aminoalkyl group or a piperidinyl group, and
• R _{28 represents} hydrogen or optionally substituted alkyl, cycloalkyl, an optionally substituted aminoalkyl group or an optionally substituted piperidinyl group, or
• R ₂₇ and R ₂₈ together with the N atom one through alkyl groups. form substituted or unsubstituted pyrrolidine, piperidine or morpholine ring, and
• R _{29 represents} hydrogen or optionally substituted alkyl.

A cation M of valence q is, for example, one from the series Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn ²⁺ , Cd ²⁺ , Al ³⁺ , Sn ²⁺ , Cr ^{3 +} , Co ²⁺ , Ni ²⁺ , an oxo complex of metal ions, in particular VO ²⁺ and MoO ₂ ²⁺ or a tin alkyl ion of the formula (R *) ₂ Sn ²⁺ , or (CH ₂ CH ₂ COOR *) ₂ Sn ^{2 +} , wherein R * is a C ₁ -C ₈ alkyl, but especially ethyl, n-propyl, and especially n-butyl; preferred as cations M ^{q +} are in particular Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Co ²⁺ , and especially Ni ²⁺ or Al ³⁺ . The coordination numbers of these cations are known to the person skilled in the art and, depending on the metal, are 4 or 6.

q is 2 or 3, especially 2.

r is 1 or 2 and corresponds to the number of enolate anions in ligand L. If the ligand L contains an enolate group, the complex generally contains q ligands L, unless a deficit of L was used in the preparation. If the ligand L contains two enolate groups, then both enolic coordination sites need not be occupied by one and the same metal center M ^{q +} . Two ligands L containing enolate groups are therefore suitable for the production of oligomeric or even polymeric molecules which are distinguished by increased extraction stability. The ratio of metal M ^{q +} to ligand L ^r- given in formula I is also correct in this case if it is calculated on the building block on which the polymer is based. Such compounds are new and have a molecular weight of approximately 400-10,000, preferably 400-2,000.

As C ₁ -C ₄ alkyl, R ₁ is branched or, in particular, unbranched alkyl, such as ethyl, n-propyl or n-butyl, but especially methyl. R ₁ is preferably hydrogen. All R ₁ preferably have the same meaning.

Z ₁ is C ₁ -C ₁₂ alkyl, for example methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl or n-dodecyl. Alkyl groups with 1-8, in particular those with 1-4 C atoms and especially methyl, are preferred.

Z ₁ as C ₃ -C ₈ alkenyl is, for example, allyl, 2-butenyl, 2-hexenyl or 2-octenyl, in particular allyl.

Z ₁ is as C ₃ -C ₄ alkynyl, for example propargyl.

If Z _{1 is} C ₂ -C ₂₁ alkoxyalkyl, the alkyl part can contain 1-3 C atoms and the alkoxy part 1-18 carbon atoms, such as in methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 3-n-butoxyethyl, 2-octoxyethyl or 2-octadecyloxyethyl. Compounds in which Z ₁ denotes an alkoxyalkyl group with 2-6 C atoms should be mentioned in particular.

Z ₁ is as C ₇ -C ₈ aralkyl, for example benzyl or α-phenylethyl.

Z ₁ is an aliphatic acyl group with 1-4 C atoms, for example formyl, acetyl, acryloyl or crotonyl, in particular acetyl.

If Z _{1 is} the group -CH ₂ COOR ₂ , R ₂ is C ₁ -C ₈ alkyl, for example methyl, ethyl, isopropyl, n-butyl, isobutyl, t-butyl, isopentyl or 'n-octyl. R ₂ is preferably C ₁ -C ₄ alkyl _: R ₂ is C ₃ -C ₆ alkenyl, for example allyl, 2-butenyl or 2-hexenyl. R ₂ is' as C _f -C ₈ aralkyl, for example benzyl or a-phenylethyl.

If Z _{1 is} the group -CH ₂ -CH (R ₃ ) -OR ₄ , R _{3 means} hydrogen, methyl or phenyl, in particular hydrogen. R ₄ is an aliphatic C ₁ -C ₁₈ acyl radical, for example. wise formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl or acryloyl. R ₄ is as aromatic C ₇ acyl residue benzoyl and as araliphatic C ₈ -C ₉ acyl residue, cinnamoyl, phenylacetyl or phenylpropionyl. The aromatic part is optionally substituted with chlorine, C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl or t-butyl or with C ₁ -C ₈ alkoxy, such as methoxy, ethoxy, butoxy or octoxy and / or hydroxy. Substituted aromatic acyl groups are, for example, chlorobenzoyl, toluoyl, isopropylbenzoyl, 2,4-dichlorobenzoyl, 4-methoxybenzoyl, 3-butoxybenzoyl, 2- Hydroxybenzoyl or 3,5-di-t-butyl-4-hydroxy-benzoyl. An araliphatic substituted acyl group is, for example, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl. If R _{4 is} an alicyclic C ₆ -C ₉ acyl group, it can be cyclohexylcarbonyl or 2,4-dimethylcyclohexylcarbonyl.

so besitzen die darin enthaltenen Symbole R₁, Z₂ und Z₃ die angegebene Bedeutung. R₁ ist in Formel IV besonders bevorzugt Wasserstoff. Bevorzugt werden Verbindungen der Formel I in denen alle im Molekül vorkommenden Reste R₁ identisch sind. Dasselbe gilt für alle Reste Z₂ und alle Reste Z₃.Z _{1 is} one of the groups - (CH ₂ ) ₄ -R ₅ ,

the symbols R ₁ , Z ₂ and Z ₃ contained therein have the meaning given. R ₁ in formula IV is particularly preferably hydrogen. Compounds of the formula I in which all the radicals R ₁ occurring in the molecule are identical are preferred. The same applies to all Z ₂ residues and all Z ₃ residues.

If Z _{1 is} a group of the formula III, then R _{6 is} a group of the formula V in which R _{9 is} C ₁ -C ₄ alkyl, such as ethyl, propyl, n-butyl, in particular methyl, and very particularly hydrogen.

R ₇ and R ₈ are as C ₂ -C ₉ alkoxymethyl, for example methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl or octoxymethyl. Preferred meaning of R ₇ and R ₈ is hydrogen or methyl. Of particular interest are compounds in which R _{7 is} hydrogen and R _{8 is} hydrogen or methyl.

X is -0- or -NR ₁₀ , preferably -0-.

Y is -0- or -NR _{10 ',} preferably -NR ₁₀ , where R _{10 is} very particularly hydrogen or methyl.

R ₁₀ as C ₁ -C ₁₂ alkyl is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl or n-dodecyl, but preferably methyl.

R ₁₀ as C ₃ -C ₈ alkenyl is, for example, allyl, 2-butenyl, 2-hexenyl or 2-octenyl, in particular allyl.

If R _{10 is} C ₃ -C ₂₁ alkoxyalkyl, the alkyl part can in particular contain 2-3 C atoms and the alkoxy part consist of 1-18 C atoms, such as 2-methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl , 3-n-butoxyethyl, 2-octoxyethyl or 2-octadecyloxyethyl ..

R ₁₀ as C ₇ -C ₁₃ aralkyl is in particular phenylethyl or especially benzyl.

If R _{10 is} phenyl, this can be mono- or disubstituted with C ₁ -C ₈ alkyl such as methyl, ethyl, propyl, butyl, hexyl or octyl, in particular methyl. R ₁₀ as phenyl can also be di- and preferably mono-substituted with C ₁ -C ₈ alkoxy, such as methoxy, ethoxy, butoxy or octoxy, in particular methoxy.

If R _{10 is} a group of the formula VI, then R _{11 can} be C ₁ -C ₁₂ alkyl, C ₃ -C ₈ alkenyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₈ aralkyl, or as an aliphatic acyl group with 1- 4 C atoms or as a group -CH ₂ COOR have the meaning given above for Z ₁ as an example.

Z ₂ can preferably denote hydrogen.

If Z _{2 is} C ₂ -C ₁₈ , preferably C ₂ -C ₁₂ and in particular C _Z -C ₇ aliphatic acyloxy, it can be acetyloxy, propionyloxy, butyryloxy, hexanoyloxy, heptanoyloxy, dodecanoyloxy or stearoyloxy.

Z ₂ as benzoyloxy can with C ₁ -C ₈ alkyl such as methyl ethyl, propyl, butyl, octyl, especially with methyl, or with C ₁ -C ₈ alkoxy such as methoxy, ethoxy, butoxy or octoxy, especially with methoxy, di- and preferably be mono-substituted; Compounds in which Z ₂ is unsubstituted as benzoyloxy are of particular interest.

Z ₂ is C ₂ -C ₁₈ acylamido, for example acetylamido, propionylamido, butyrylamido, hexanoylamido, heptanoylamido, dodecanoylamido or stearoylamido. Acylamido groups with 2-12, and especially those with 2-7, carbon atoms are preferred.

If Z _{2 is} a C ₁ -C ₈ N-alkyl-substituted C ₂ -C ₁₈ acylamido group, the possible N-alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, n-hexyl or n-octyl.

If Z _{2 contains} a radical R ₁₂ , this can be linked to the piperidine ring directly or preferably via an alkylene group with 2-10 C atoms, preferably 2-6 C atoms, such as dimethylene, trimethylene, tetramethylene, hexamethylene or decamethylene. Connections via a xylylene or bitolylene bridge are just as preferred as alkylene bridges.

Z ₂ can be a group of the formula VIII, in which R ₁₃ as alkylene can have, for example, 1-8, preferably 1-6, carbon atoms, such as methylene, dimethylene, trimethylene, tetramethylene, hexamethylene or octamethylene. However, the index e can also preferably mean 0, ie the alkylene group can also be absent.

X 'is -O- or -NR ₁₄ , wherein R ₁₄ is C ₁ -C ₄ alkyl, ethyl, propyl or butyl, and the preferred meaning of R _{14 is} hydrogen or methyl.

R ₁₃ can also be a group - (R ₁₅ ) C (R ₁₆ ) -, where R ₁₅ and R _{16 are} C ₁ -C ₁₂ , preferably C ₁ -C ₄ alkyl, such as methyl, ethyl, propyl, butyl, hexyl, Can be octyl or dodecyl.

^R ₁₅ and ^R ₁₆ are as C ₃ -C ₈ alkenyl, for example allyl, 2-butenyl, 2-hexenyl or 2-octenyl, in particular allyl.

R ₁₅ and ^R ₁₆ as C ₇ -C ₁₁ aralkyl are especially phenylethyl or in particular benzyl.

R ₁₅ and R ₁₆ can be cyanoethyl and especially cyanomethyl.

R ₁₈ can be in the groups of the formulas IX or X as C ₁ -C ₈ alkyl, for example methyl, ethyl, propyl, butyl, hexyl or octyl. However, R ₁₈ is preferably hydrogen.

R ₁₉ in formula X may be C ₁ -C ₈ alkyl, preferably C ₁ -C ₄ alkyl, for example methyl, ethyl, n-propyl, n-butyl, hexyl or octyl. R ₁₉ also preferably denotes hydrogen, allyl or benzyl.

In formula XI, R ₂₀ is C ₁ -C ₄ alkyl, for example methyl, ethyl, n-propyl or n-butyl. However, a group of formula V should be mentioned as the preferred meaning of R ₂₀ .

R ₂₁ in the formula XI is particularly preferably C ₂ -C ₆ alkylene such as dimethylene, trimethylene, tetramethylene or hexamethylene. However, it can preferably also mean cyclohexylidene or phenylene.

If Z _{2 represents} a group of the formula XII, the indices a ', b' and g contained therein are preferably 0.

R ₂₂ and R ₂₃ in the formulas XIII and XIV can be, for example, methyl, ethyl, propyl or butyl as C ₁ -C ₄ alkyl, preference being given to ethyl and especially methyl, and also hydrogen.

Z ₂ and Z ₃ together form a heterocycle are as before. all groups of the formula XV and XVI preferred.

R ₂₄ is ethyl, preferably methyl and especially hydrogen.

^R ₂₅ is as C ₁ -C ₁₂ alkyl, for example methyl, ethyl, propyl, butyl, hexyl ,. Octyl, decyl, or dodecyl. Alkyl groups with 1-8 C atoms are preferred.

R ₂₅ is. as aralkyl with 7-8 carbon atoms, especially phenylethyl or especially benzyl.

R ₂₅ is as C ₃ -C ₈ alkenyl, for example allyl, 2-butenyl, 2-hexenyl or 2-octenyl, in particular allyl.

R ₂₆ is as C ₁ -C ₁₈ alkyl, for example methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl or octadecyl. Preferred alkyl are those with 1-12, in particular 1-8 C atoms, and especially those with 1-4 C atoms.

If A is an amine of the formula XVIII, then be. mean its substituents R ₂₇ , R ₂₈ and R _29, for example C ₁ -C ₁₈ alkyl, such as methyl, ethyl, isopropyl, sec-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl or n- Octadecyl, preferably C ₁ -C ₈ alkyl.

If it is substituted alkyl, it means in particular C ₁ -C ₁₈ hydroxyalkyl, such as 1-hydroxyethyl, 1-hydroxypropyl, 1-hydroxy-1-methyl-ethyl, 3-hydroxy-pentyl, or 1-hydroxy- 2-methyl-ethyl, preferably C ₁ -C ₈ hydroxyalkyl.

R ₂₇ and R ₂₈ can also mean C ₅ -C ₁₂ and in particular C ₅ -C ₆ cycloalkyl, which can be, for example, cyclopentyl, cyclohexyl, 4-methylcyclohexyl or 4-tert-butylcyclohexyl. R ₂₇ can also have the meaning of optionally substituted C ₆ -C ₁₀ aryl, which can be, for example, phenyl, tolyl, xylyl, tert-butylphenyl or dodecylphenyl. R ₂₇ as C ₇ -C ₂₀ aralkyl is, for example, benzyl, 4-methylbenzyl, 4-t-butylbenzyl or 4-dodecylbenzyl, in particular benzyl.

worin R₁, R₁₁ und R₁₄ die oben angegebene Bedeutung haben und v eine ganze Zahl von 1 bis 8 ist.If R ₂₇ and R _{28 are} an optionally substituted aminoalkyl group, it is in particular an aminoalkyl group substituted by a piperidinyl group, for example of the formula VIIb

wherein R ₁ , R ₁₁ and R _{14 have} the meaning given above and v is an integer from 1 to 8.

If R27 and R _{28 are} an optionally substituted piperidinyl group, it is preferably one of the formula VI.

R ₂₇ and R28 together with the N atom of the amine of the formula XVIII can form a pyrrolidine, piperidine or morpholine ring which is substituted or unsubstituted by alkyl groups. It may be examples in diesem.Fall 'game, be a 2,5-dimethylpyrrolidine _-, 4-methylpiperidine, 2,2,6,6-tetramethylpiperidine, 2,6-dimethylmorpholine, pyrrolidine, piperidine or morpholine ring act, in particular a 2,2,6-, 6-tetramethylpiperidine ring.

m can be 0, 1 or 2, preferably m means 0.

In its meaning as an amine, the ligand A is by definition a primary, secondary or tertiary amine which is capable of forming a complex with the metal chelates mentioned above. Examples of such amines are: n-butylamine, n-dodecylamine, β-ethylhexylamine, benzylamine, 4-octylbenzylamine, dibutylamine, dicyclohexylamine, dioctadecylamine, morpholine, 2,2,6,6-tetramethylpiperidine, N-ethylaniline, tri-n- octylamine, N, N-dimethylaniline, N, N-dimethylcyclohexylamine, N-ethylpiperidine, N-methylpyrrolidine, dibenzylpropylamine, N-benzyl-2,5-dimethylpyrrolidine, 4-dimethylamino-2,2,6-, 6- tetramethylpiperidine, 6-dimethyismino-1,2,3 6,6-ponsamethyl-piperidine, N, N'-methyl-N, N '- (1,2,2,6,6-pentamethyl-4-piperidyl) ethylenediamine , Hydroxyethylamine, di- (hydroxyethyl) amine, tri- (hydroxyethyl) amine, tri- (2-hydroxypropyl) amine, N-phenyl-N, N-di- (hydroxyethyl) amine or hydroxypropylamine .

The complexes of the formula I ^{according to the invention contain} 0 to 2 moles of the amine ligand A per mole of metal M ^q⊕ , which can be replaced in whole or in part by water. The mole fraction expressed by m in formula I thus consists of the sum of m 'moles of amine ligand and m "moles of water, which mole fractions expressed by m' and m" need not be an entire number. Preferred complexes are those with a low water content, since these dissolve better in non-polar polymers than more hydrated complexes. m 'thus approximately assumes the value of m.

An amine ligand A is only necessary if the coordination number of the metal center is not satisfied by the chelating agent L alone.

• M^q⊕ Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, Cd²⁺, Al³⁺, Sn²⁺, Cr³⁺, Co²⁺, Ni²⁺, VO²⁺, MoO²⁺, (R*)₂Sn²⁺ oder (CH₂CH₂COOR)₂Sn²⁺ bedeutet, worin
• R* C₁-C₈ Alkyl ist, und
• q 2 oder 3 ist, und
• r 1 oder 2 ist, wobei der Quotient q/r 1, 1.5, 2 oder 3 bedeutet, und
• L eine Gruppe der Formel II ist, worin eine Gruppe der Formel II ist, worin
• R₁ Wasserstoff oder Methyl ist, und
• Z₁ Wasserstoff, C₁-C₈ A lkyl, C₃-C₄ Alkenyl, C₃ Alkinyl, C₂-C₁₀ Alkoxyalkyl, C₇-C₈ Aralkyl, Acetyl oder eine der Gruppen -CH₂COOR₂ oder ―CH₂-CH(R₃)-OR₄, oder einen Rest -(CH₂)₄-R₅,
  
  
  oder eine Gruppe der Formel III bedeutet, wobei
• ^R ₂ C₁-C₄ Alkyl, C₃-C₄ Alkenyl, Phenyl, C₇-C₈ Aralkyl oder Cyclohexyl ist, und
• R₃ Wasserstoff oder Methyl ist,
• R₄ eine aliphatische Acylgruppe mit 1-12 C-Atomen ist, und
• _R5 eine Gruppe der Formel IV ist, worin Z₂ und Z₃ die unten angegebene Bedeutung haben und R₁ Was- werstoff ist, und
• R₆ eine Gruppe der Formel V bedeutet, worin Rg Wasserstoff oder Methyl ist, und
• R₇ und R₈ unabhängig voneinander Wasserstoff oder Methyl sind, und
• a 0, 1 oder 2, und
• b 0 oder 1, und
• c 0 oder, falls a und/oder b verschieden von 0 sind, auch 1 ist, und
• X -0- ist, und
• Y -0- oder -N-R₁₀ ist, wobei
• R₁₀ Wasserstoff oder Methyl oder falls a, b und c 1, R₇ Wasserstoff und Y -0- sind, auch eine Gruppe -CH₂-CH₂-OR₆, worin R₆ die oben angegebene Bedeutung hat, bedeutet, und
• Z₂ Wasserstoff, C₂-C₁₂ aliphatischer Acyloxy, gegebenenfalls mit Methyl oder Methoxy mono- oder disubstituiertes Benzoyloxy, oder eine gegebenenfalls C₁-C₄ N-alkylsubstituierte C₂-C₁₂ Acylamidogruppe ist, oder eine der Gruppen-R₁₂,
  
  oder
  
  ist, worin d 2 bis 6 ist, und
• R₁₂ eine Gruppe der Formel VII ist, worin R₁ und Z₁ die oben angegebene Bedeutung haben, oder
• Z₂ ferner eine Gruppe der Formel VIII bedeutet, worin
• X' -O- oder -N-R₁₄ ist, wobei
• R₁₄ Wasserstoff oder C₁-C₄ Alkyl ist, und
• R₁₃ -(CH₂)_e- oder eine Gruppe
  
  ist, wobei
• e 0 bis 8 ist, und
• R₁₅ undR ₁₆ unabhängig voneinander Wasserstoff, C₁-C₄ Alkyl, Allyl, Benzyl, Cyanomethyl, Cyanoäthyl oder eine Gruppe -CH₂COOR₁₇, wobei
• R₁₇ Methyl oder Aethyl ist, bedeucen, oder
• Z₂ eine Gruppe der Formeln IX, X oder XI ist, vorin
• R₆ und R₇ die oben angegebene Bedeutung haben,
• R₁₈ Wasserstoff bedeutet,
• R₁₉ Wasserstoff, C₁-C₄ Alkyl, Allyl oder Benzyl ist,
• R₂₀ C₁ -C₄ Alkyl oder eine Gruppe der Formel V mit oben angegebener bedeutung ist, und
• R₂₁ C₂-C₆ Alkylen, Cyclohexyliden oder Phenylen oder
• Z₂ ferner eine Gruppe der Formel XIIa
  
  ist, worin
• a, b, c, R₆ und R₇ oben angegebene Bedeutung haben, und
• f 0 oder 1 ist, und
• X₁ -0- oder
  
  bedeutet, worin
• 
  Wasserstoff, C₁-C₁₂ Alkyl, Cyclohexyl, C₃-C₁₄ Alkoxyalkyl, C₇-C₈ Aralkyl, gegebenenfalls mit C₁-C₃ Alkyl und/oder C₁-C₈ Alkoxy mono- oder disubstituiertes Phenyl oder falls a, b und c 1, R₇ Wasserstoff und Y -0- sind, auch eine Gruppe -CH₂-CH₂-OR₆, worin R₆ die oben angegebene Bedeutung hat, ist, und
  
  ferner eine Gruppe VI bedeutet, worin
• R₁ die oben angegebene Bedeutung hat,
• R₁₁ Wasserstoff, Methyl oder Allyl ist, und
• Y₁ -₀- oder
  
  bedeutet, worin
• 
  Wasserstoff, C₁-C₈ Alkyl oder Phenyl ist, oder
• Z₂ ferner eine der Gruppen XIII oder XIV ist, worin
• R₆ die oben angegebene Bedeutung hat, und
• R₂₂undR₂₃ unabhängig voneinander Wasserstoff, Methyl oder Aethyl sind, und
• Z₃ Wasserstoff oder Cyano ist, oder
• Z₂ und Z₃ zusammen eine der Formeln XV, XVI oder XVII bedeuten, worin R₆ die oben angegebene Bedeutung hat, und
• R₂₄ Wasserstoff, Methyl oder Aethyl ist und
• R₂₅ Wasserstoff, C₁-C₁₂ Alkyl, C₃-C₈ Alkenyl, eine Gruppe -CH₂COOR₂₆ oder -CH₂-CH(R₈)-OR₆ bedeutet, wobei R₆ und R₈ die oben angegebene Bedeutung haben, und
• R₂₆ C₁-C₁₂ Alkyl ist, und
• m 0, 1 oder 2 ist, und
• A H₂O oder ein Amin der Formel XVIII ist, worin
• R₂₇ gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl, C₅-C₁₂ Cycloalkyl, gegebenenfalls mit C₁-C₁₂ Alkyl substituiertes C₆-C₁₀ Aryl, C₇-C₂₀ Aralkyl, eine gegebenenfalls substituierte Aminoalkylgruppe mit 1-8 C-Atomen im Alkylteil oder Piperidinylgruppe ist, und
• R₂₈ Wasserstoff, oder gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl, C₅-C₁₂ Cycloalkyl oder eine gegebenenfalls substituierte Aminoalkylgruppe mit 1-8 C-Atomen im Alkylteil oder Piperidinylgruppe bedeutet, oder
• R₂₇undR₂₈ zusammen mit dem N-Atom einen durch Alkylgruppen substituierten oder unsubstituierten Pyrrolidin-, Piperidin- oder Morpholinring bilden, und
• R₂₉ Wasserstoff oder gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl bedeutet.

Preferred compounds of formula I are those in which

• M ^q ⊕ Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn ²⁺ , Cd ²⁺ , Al ³⁺ , Sn ²⁺ , Cr ³⁺ , Co ²⁺ , Ni ²⁺ , VO ²⁺ , MoO ²⁺ , (R *) ₂ Sn ²⁺ or (CH ₂ CH ₂ COOR) ₂ Sn ²⁺ , wherein
• R * is C ₁ -C ₈ alkyl, and
• q is 2 or 3, and
• r is 1 or 2, the quotient q / r being 1, 1.5, 2 or 3, and
• L is a group of formula II, wherein is a group of formula II, wherein
• R _{1 is} hydrogen or methyl, and
• Z _{1 is} hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₄ alkenyl, C ₃ alkynyl, C ₂ -C ₁₀ alkoxyalkyl, C ₇ -C ₈ aralkyl, acetyl or one of the groups -CH ₂ COOR ₂ or ―CH ₂ -CH (R ₃ ) -OR ₄ , or a radical - (CH ₂ ) ₄ -R ₅ ,
  
  
  or a group of the formula III, where
• ^R _{2 is} C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl, and
• R _{3 is} hydrogen or methyl,
• R _{4 is} an aliphatic acyl group with 1-12 C atoms, and
• _{R5 is} a group of the formula IV, in which Z ₂ and Z _{3 have} the meaning given below and R _{1 is} hydrogen, and
• R _{6 represents} a group of formula V, wherein Rg is hydrogen or methyl, and
• R ₇ and R _{8 are} independently hydrogen or methyl, and
• a 0, 1 or 2, and
• b 0 or 1, and
• c is 0 or, if a and / or b are different from 0, is also 1, and
• X is -0-, and
• Y is -0- or -NR ₁₀ , where
• R _{10 is} hydrogen or methyl or if a, b and c 1, R _{7 are} hydrogen and Y is -0-, also a group -CH ₂ -CH ₂ -OR ₆ , in which R _{6 has} the meaning given above, and
• Z _{2 is} hydrogen, C ₂ -C ₁₂ aliphatic acyloxy, optionally benzoyloxy mono- or disubstituted with methyl or methoxy, or a given one if C ₁ -C ₄ N-alkyl-substituted C ₂ -C _{12 is} acylamido group, or one of the groups R ₁₂ ,
  
  or
  
  where d is 2 to 6, and
• R _{12 is} a group of the formula VII, in which R ₁ and Z _{1 have} the meaning given above, or
• Z ₂ also denotes a group of the formula VIII, in which
• X 'is -O- or -NR ₁₄ , where
• R _{14 is} hydrogen or C ₁ -C ₄ alkyl, and
• R ₁₃ - (CH ₂ ) _e - or a group
  
  is where
• e is 0 to 8, and
• R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₄ alkyl, allyl, benzyl, cyanomethyl, cyanoethyl or a group -CH ₂ COOR ₁₇ , where
• R _{17 is} methyl or ethyl, depress, or
• Z _{2 is} a group of the formulas IX, X or XI
• R ₆ and R _{7 have} the meaning given above,
• R _{18 represents} hydrogen,
• R _{19 is} hydrogen, C ₁ -C ₄ alkyl, allyl or benzyl,
• R _{20 is} C ₁ -C ₄ alkyl or a group of formula V with the meaning given above, and
• R ₂₁ C ₂ -C ₆ alkylene, cyclohexylidene or phenylene or
• Z ₂ also a group of formula XIIa
  
  is what
• a, b, c, R ₆ and R ₇ have the meaning given above, and
• f is 0 or 1, and
• X ₁ -0- or
  
  means what
• 
  Hydrogen, C ₁ -C ₁₂ alkyl, cyclohexyl, C ₃ -C ₁₄ alkoxyalkyl, C ₇ -C ₈ aralkyl, optionally mono- or disubstituted phenyl with C ₁ -C ₃ alkyl and / or C ₁ -C ₈ alkoxy or if a , b and c 1, R _{7 are} hydrogen and Y is -0-, also a group -CH ₂ -CH ₂ -OR ₆ , in which R _{6 has} the meaning given above, and
  
  furthermore means a group VI, wherein
• R _{1 has} the meaning given above,
• R _{11 is} hydrogen, methyl or allyl, and
• Y ₁ - ₀ - or
  
  means what
• 
  Is hydrogen, C ₁ -C ₈ alkyl or phenyl, or
• Z _{2 is} also one of groups XIII or XIV, wherein
• R _{6 has} the meaning given above, and
• R _{22 and} R _{23 are} independently hydrogen, methyl or ethyl, and
• Z _{3 is} hydrogen or cyano, or
• Z ₂ and Z ₃ together mean one of the formulas XV, XVI or XVII, in which R _{6 has} the meaning given above, and
• R _{24 is} hydrogen, methyl or ethyl and
• R _{25 is} hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₈ alkenyl, a group -CH ₂ COOR ₂₆ or -CH ₂ -CH (R ₈ ) -OR ₆ , where R ₆ and R _{8 have} the meaning given above have and
• R _{26 is} C ₁ -C ₁₂ alkyl, and
• m is 0, 1 or 2, and
• AH ₂ O or an amine of formula XVIII, wherein
• R ₂₇ C ₁ -C ₁₈ alkyl optionally substituted with -OH, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₁₀ aryl optionally substituted with C ₁ -C ₁₂ alkyl, C ₇ -C ₂₀ aralkyl, an optionally substituted aminoalkyl group with 1 -8 carbon atoms in the alkyl part or piperidinyl group, and
• R _{28 denotes} hydrogen, or C ₁ -C ₁₈ alkyl optionally substituted with -OH, C ₅ -C ₁₂ cycloalkyl or an optionally substituted aminoalkyl group with 1-8 C atoms in the alkyl part or piperidinyl group, or
• R _{27 and} R ₂₈ together with the N atom form an alkyl group-substituted or unsubstituted pyrrolidine, piperidine or morpholine ring, and
• R _{29 is} hydrogen or C ₁ -C ₁₈ alkyl optionally substituted with -OH.

• M^q⊕ Ca²⁺, Mg²⁺, Zn²⁺, Co²⁺, Ni²⁺ oder Al³⁺ ist, und
• q 2 oder 3 ist, und
• r 1 oder 2 ist, wobei der Quotient q/r 1, 1.5, 2 oder 3 ist, und
• L eine Gruppe der Formel II ist, worin
• R₁ Wasserstoff oder Methyl ist, und
• Z₁ Wasserstoff, C₁-C₄ Alkyl, Allyl, C₂-C₆ Alkoxyalkyl, Benzyl, Acetyl oder eine der Gruppen -CH₂COOR₂ oder -CH₂-CH(R₃)-OR₄ oder eine Gruppe der Formel III bedeutet, wobei
• R₂ C₁-C₄ Alkyl ist, und
• R₃ Wasserstoff ist, und
• R₄ eine aliphatische Acylgruppe mit 1-8 C-Atomen ist, und
• R₆ eine Gruppe der Formel V bedeutet, worin R₉ Wasserstoff ist, und
• ^R ₇ Wasserstoff ist, und
• R₈ Wasserstoff oder Methyl bedeutet, und
• a 0, 1 oder 2 ist, und
• b 0 oder 1 ist, und
• c 0 oder, fa.lls a und/oder b von 0 verschieden sind, auch 1 ist, und
• X -0- ist, und
• Y -0- oder -N-R₁₀ bedeutet, wobei
• R₁₀ Wasserstoff oder Methyl oder, falls a, b und c 1, und Y -0- sind auch eine Gruppe -CH₂-CH₂-OR₆, worin R₆ die oben angegebene-Bedeutung hat, ist, und
• Z₂ Wasserstoff, C₂-C₇ aliphatisches Acyloxy,'gegebenenfalls mit Methyl oder Methoxy monosubstituiertes Benzoyloxy, oder eine gegebenenfalls mit Methyl N-substituierte C₂-C₇ Acylamidogruppe ist oder eine der Gruppen -(CH₂)_d-R₁₂,
  
  ist, worin d 2 bis 6 ist, und
• R₁₂ eine Gruppe der Formel VII ist, worin R₁ und Z₁ die oben angegebene Bedeutung haben, oder
• Z₂ ferner eine Gruppe der Formel VIII bedeutet, worin
• X' -0- oder -N-N₁₄ ist, wobei
• R₁₄ Wasserstoff oder Methyl ist, und
• R₁₃ -(CH₂)_e- oder eine Gruppe
  
  ist, wobei
• e 0 bis 8 ist, und
• R₁₅undR₁₆ unabhängig voneinander Wasserstoff, C₁-C₄ Alkyl, Allyl, Benzyl oder Cyanomethyl sind, oder
• Z₂ ferner eine Gruppe der Formel XI ist, worin
• R₂₀ eine Gruppe derFormel V mit oben angegebener Bedeutung ist, und
• R₂₁ C₂-C₆ Alkylen oder Phenylen bedeutet, oder
• Z₂ ferner eine Gruppe der Formel XIIa ist, worin a, b, c, R₆ und R₇ oben angegebene Bedeutung .haben, und
• f 0 oder 1 ist, und
• X₁ -O- oder
  
  bedeutet, worin
• 
  Wasserstoff, C₁-C₈ Alkyl, Cyclohexyl, C₃-C₈ Alkoxyalkyl, C₇-C₈ Aralkyl, gegebenenfalls mit C₁-C₃ Alkyl und/oder C₁-C₂ Alkoxy monosubstituiertes Phenyl oder falls a, b und c 1 und Y₁ -O- sind, auch eine Gruppe -CH₂-CH₂-OR₆, worin R₆ die oben angegebene Bedeutung hat, ist, und
  
  ferner eine Gruppe VI bedeutet, worin
• R₁ die oben angegebene Bedeutung hat, und
• R₁₁ Wasserstoff oder Methyl ist, und
• Y₁ -0- oder
  
  bedeutet, worin
• 
  Wasserstoff, C₁-C₄ Alkyl oder Phenyl ist, oder
• Z₂ ferner eine der Gruppen XIII oder XIV ist, worin
• R₆ die oben angegebene Bedeutung hat, und
• R₂₂undR₂₃ unabhängig voneinander Wasserstoff, Methyl oder Aethyl sind, und
• Z₃ Wasserstoff ist, oder
• Z₂ und Z₃ zusammen eine der Formeln XV, XVI oder XVII bedeuten, worin R₆ die oben angegebene Bedeutung hat, und
• R₂₄ Wasserstoff oder Methyl ist, und
• R₂₅ C₁-C₈ Alkyl, Allyl, oder eine der Gruppen -CH₂-COOR₂₆ oder -CH₂-CH(R₈)-OR₆ bedeutet, worin R₆ und R₈ die oben angegebene Bedeutung haben, und
• R₂₆ C₁-C₈ Alkyl ist, und .
• m 0, 1 oder 2 ist, und
• A H₂O oder ein Amin der Formel XVIII ist, worin
• R₂₇undR₂₈ unabhängig voneinander C₁-C₈ Alkyl, C₁-C₆ Hydroxyalkyl oder eine substituierte Aminoalkylgruppe der Formel VIIb
  
  ist, worin R₁, R₁₁ und R₁₄ die oben angegebene Bedeutung haben und v 1 bis 8 ist, oder
• R₂₇undR₂₈ zusammen mit dem N-Atom eine Piperidingruppe bil- den, und
• R₂₉ Wasserstoff, C₁-C₈ Alkyl oder C₁-C₆ Hydroxyalkyl ist.

Compounds of the formula I in which

• M ^q ⊕ Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al ³⁺ , and
• q is 2 or 3, and
• r is 1 or 2, the quotient q / r being 1, 1.5, 2 or 3, and
• L is a group of formula II, wherein
• R _{1 is} hydrogen or methyl, and
• Z _{1 is} hydrogen, C ₁ -C ₄ alkyl, allyl, C ₂ -C ₆ alkoxyalkyl, benzyl, acetyl or one of the groups -CH ₂ COOR ₂ or -CH ₂ -CH (R ₃ ) -OR ₄ or a group of the formula III means where
• R _{2 is} C ₁ -C ₄ alkyl, and
• R _{3 is} hydrogen, and
• R _{4 is} an aliphatic acyl group with 1-8 C atoms, and
• R _{6 represents} a group of formula V, wherein R _{9 is} hydrogen, and
• ^R _{7 is} hydrogen, and
• R _{8 represents} hydrogen or methyl, and
• a is 0, 1 or 2, and
• b is 0 or 1, and
• c is 0 or, fa.lls a and / or b are different from 0, is also 1, and
• X is -0-, and
• Y means -0- or -NR ₁₀ , where
• R _{10 is} hydrogen or methyl or, if a, b and c 1, and Y -0- are also a group -CH ₂ -CH ₂ -OR ₆ , in which R _{6 has} the meaning given above, and
• Z _{2 is} hydrogen, C ₂ -C ₇ aliphatic acyloxy, 'benzoyloxy optionally monosubstituted with methyl or methoxy, or an C ₂ -C ₇ acylamido group optionally substituted with methyl N or one of the groups - (CH ₂ ) _d -R ₁₂ ,
  
  where d is 2 to 6, and
• R _{12 is} a group of the formula VII, in which R ₁ and Z _{1 have} the meaning given above, or
• Z ₂ also denotes a group of the formula VIII, in which
• X 'is -0- or -NN ₁₄ , where
• R _{14 is} hydrogen or methyl, and
• R ₁₃ - (CH ₂ ) _e - or a group
  
  is where
• e is 0 to 8, and
• R _{15 and} R _{16 are} independently hydrogen, C ₁ -C ₄ alkyl, allyl, benzyl or cyanomethyl, or
• Z _{2 is} also a group of formula XI, wherein
• R _{20 is} a group of formula V as defined above, and
• R _{21 is} C ₂ -C ₆ alkylene or phenylene, or
• Z _{2 is} also a group of the formula XIIa, in which a, b, c, R ₆ and R _{7 have the} meaning given above, and
• f is 0 or 1, and
• X ₁ -O- or
  
  means what
• 
  Hydrogen, C ₁ -C ₈ alkyl, cyclohexyl, C ₃ -C ₈ alkoxyalkyl, C ₇ -C ₈ aralkyl, optionally phenyl monosubstituted with C ₁ -C ₃ alkyl and / or C ₁ -C ₂ alkoxy or if a, b and c 1 and Y _{1 are} -O-, also a group -CH ₂ -CH ₂ -OR ₆ , in which R _{6 has} the meaning given above, and
  
  furthermore means a group VI, wherein
• R _{1 has} the meaning given above, and
• R _{11 is} hydrogen or methyl, and
• Y ₁ -0- or
  
  means what
• 
  Is hydrogen, C ₁ -C ₄ alkyl or phenyl, or
• Z _{2 is} also one of groups XIII or XIV, wherein
• R _{6 has} the meaning given above, and
• R _{22 and} R _{23 are} independently hydrogen, methyl or ethyl, and
• Z _{3 is} hydrogen, or
• Z ₂ and Z ₃ together mean one of the formulas XV, XVI or XVII, in which R _{6 has} the meaning given above, and
• R _{24 is} hydrogen or methyl, and
• R ₂₅ C ₁ -C ₈ alkyl, allyl, or one of the groups -CH ₂ -COOR ₂₆ or -CH ₂ -CH (R ₈ ) -OR ₆ , in which R ₆ and R _{8 have} the meaning given above, and
• R _{26 is} C ₁ -C ₈ alkyl, and.
• m is 0, 1 or 2, and
• AH ₂ O or an amine of formula XVIII, wherein
• R _{27 and} R ₂₈ independently of one another are C ₁ -C ₈ alkyl, C ₁ -C ₆ hydroxyalkyl or a substituted aminoalkyl group of the formula VIIb
  
  is where R ₁ , R ₁₁ and R _{14 have} the meaning given above and v is 1 to 8, or
• R _{27 and} R ₂₈ together with the N atom form a piperidine group, and
• R _{29 is} hydrogen, C ₁ -C ₈ alkyl or C ₁ -C ₆ hydroxyalkyl.

• M^q⊕ Ca²⁺, Mg²⁺, Zn²⁺, Co²⁺, Ni²⁺ oder Al³⁺ ist, und
• q 2 oder 3 ist, und
• r 1 oder 2 ist, wobei der Quotient q/r 1, 1.5, 2 oder 3 ist, und
• L eine Gruppe der Formel II ist, worin
• R₁ Wasserstoff ist, und
• Z₁ Wasserstoff, Methyl, Acetyl oder eine Gruppe der . Formel III bedeutet, wobei
• R₆ eine Gruppe der Formel V bedeutet, worin R₉ Was- serstoff ist, und
• R₇ Wasserstoff und
• R₈ Wasserstoff oder Methyl ist, und
• a 0, 1 oder 2 ist, und
• b 0 oder 1 und
• c 0 oder, falls a und/oder b von 0 verschieden sind, auch 1 ist,
• X -0- ist, und
• Y -N-R₁₀ bedeutet, wobei
• R₁₀ Wasserstoff ist, und
• Z₂ Wasserstoff, C₂-C₇ aliphatisches Acyloxy, Benzoyloxy, eine gegebenenfalls mit Methyl N-substituierte Acylamidogruppe ist, oder eine der Gruppen
  
  oder
  
  ist, worin d 2 bis 6 ist, und
• R₁₂ eine Gruppe der Formel VII ist, worin R₁ und Z₁ die oben angegebene Bedeutung haben, oder
• Z₂ ferner eine Gruppe der Formel VIII ist, worin
• X' -₀- oder -N-R₁₄ bedeutet, wobei
• R₁₄ Wasserstoff oder Methyl ist, und
• R₁₃ -(CH₂)_e- oder eine Gruppe
  
  .ist, wobei
• e 0 bis 8 ist, und
• R₁₅undR₁₆ unabhängig voneinander Wasserstoff, C₁-C₄ Alkyl, Allyl oder Benzyl sind, oder
• Z₂ ferner eine Gruppe der Formel XI ist, worin
• R₂₀ eine Gruppe der Formel V mit oben angegebener Bedeutung ist, und
• R₂₁ C₂-C₆ Alkylen ist, oder
• Z2 ferner eine Gruppe der Formel XIIa ist, worin a, b, c, R₆ und R8 oben angegebene Bedeutung haben, und
• f 0 oder 1 ist, und
• X₁ -O- oder
  
  bedeutet, worin
• 
  Wasserstoff, C₁-C₈ Alkyl, C₃-C₆ Alkoxyalkyl, C₇-C₈ Aralkyl, gegebenenfalls mit Methyl, Metho: oder Aethoxy monosubstituiertes Phenyl oder eine Gruppe VI bedeutet, worin
• R₁ die oben angegebene Bedeutung hat, und
• R₁₁ Wasserstoff oder Methyl ist, und
• Y₁ -0- ist, oder
• Z₂ ferner eine der Gruppen XIII oder XIV ist, worin
• R₆ die oben angegebene Bedeutung hat, und
• R₂₂undR₂₃ unabhängig voneinander Wasserstoff oder Methyl sind, und
• Z₃ Wasserstoff ist, oder
• Z₂ und Z₃ zusammen eine der Formeln XV, XVI oder XVII bedeuten, worin R₆ die oben angegebene Bedeutung hat, und
• ^R ₂₄ Wasserstoff ist, und
• _R25 C₁-C₈ Alkyl, oder eine der Gruppen -CH₂C^OO^R ₂₆ oder -CH₂-CH(R₈)-OR₆ bedeutet, worin R₆ und R₈ oben angegebene Bedeutung haben, und
• R₂₆ C₁-C₄ Alkyl ist, und
• m 0, 1 oder 2 ist, und
• A H₂0 oder ein Amin der Formel XVIII ist, worin R₂₇undR₂₈ unabhängig voneinander C₁-C₈ Alkyl, C₁-C₆ Hydroxyalkyl oder eine Gruppe VIIb sind, worin R₁, R₁₁ und R₁₄ die angegebene Bedeutung haben, und v 1 bis 8 ist, oder
• R₂₇undR₂₈ zusammen mit dem N-Atom eine Piperidingruppe bi den, und
• R29 Wasserstoff, C₁-C₈ Alkyl oder C₁-C₆ Hydroxyalky - ist.

Particular interest is given to compounds of the formula I in which

• M ^q ⊕ Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al ³⁺ , and
• q is 2 or 3, and
• r is 1 or 2, the quotient q / r being 1, 1.5, 2 or 3, and
• L is a group of formula II, wherein
• R _{1 is} hydrogen, and
• Z _{1 is} hydrogen, methyl, acetyl or a group of. Formula III means, wherein
• R _{6 represents} a group of formula V, in which R ₉ was is hydrogen, and
• R _{7 is} hydrogen and
• R _{8 is} hydrogen or methyl, and
• a is 0, 1 or 2, and
• b 0 or 1 and
• c is 0 or, if a and / or b are different from 0, is also 1,
• X is -0-, and
• Y means -NR ₁₀ , where
• R _{10 is} hydrogen, and
• Z _{2 is} hydrogen, C ₂ -C ₇ aliphatic acyloxy, benzoyloxy, an acylamido group optionally substituted with methyl N, or one of the groups
  
  or
  
  where d is 2 to 6, and
• R _{12 is} a group of the formula VII, in which R ₁ and Z _{1 have} the meaning given above, or
• Z _{2 is} also a group of formula VIII, wherein
• X 'denotes ₀ or NR ₁₄ , where
• R _{14 is} hydrogen or methyl, and
• R ₁₃ - (CH ₂ ) _e - or a group
  
  .is where
• e is 0 to 8, and
• R _{15 and} R _{16 are} independently hydrogen, C ₁ -C ₄ alkyl, allyl or benzyl, or
• Z _{2 is} also a group of formula XI, wherein
• R _{20 is} a group of formula V with the meaning given above, and
• R _{21 is} C ₂ -C ₆ alkylene, or
• Z2 is also a group of the formula XIIa, in which a, b, c, R ₆ and R8 have the meaning given above, and
• f is 0 or 1, and
• X ₁ -O- or
  
  means what
• 
  Is hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ alkoxyalkyl, C ₇ -C ₈ aralkyl, optionally phenyl monosubstituted with methyl, metho: or ethoxy or a group VI, in which
• R _{1 has} the meaning given above, and
• R _{11 is} hydrogen or methyl, and
• Y _{1 is} -0-, or
• Z _{2 is} also one of groups XIII or XIV, wherein
• R _{6 has} the meaning given above, and
• R _{22 and} R _{23 are} independently hydrogen or methyl, and
• Z _{3 is} hydrogen, or
• Z ₂ and Z ₃ together mean one of the formulas XV, XVI or XVII, in which R _{6 has} the meaning given above, and
• ^R _{24 is} hydrogen, and
• _{R25 is} C ₁ -C ₈ alkyl, or one of the groups -CH ₂ C ^O O ^R ₂₆ or -CH ₂ -CH (R ₈ ) -OR ₆ , in which R ₆ and R ₈ have the meaning given above, and
• R _{26 is} C ₁ -C ₄ alkyl, and
• m is 0, 1 or 2, and
• AH _{2 is} 0 or an amine of the formula XVIII, in which R _{27 and} R _{28 are} independently C ₁ -C ₈ alkyl, C ₁ -C ₆ hydroxyalkyl or a group VIIb, in which R ₁ , R ₁₁ and R _{14 have} the meaning given , and v is 1 to 8, or
• R _{27 and} R ₂₈ together with the N atom form a piperidine group, and
• R29 is hydrogen, C ₁ -C ₈ alkyl or C ₁ -C ₆ hydroxyalky.

• 2,3,6-Trimethyl-2,6-diäthyl-4-(1',3'-dioxobutyl- oxy)-piperidin
• 2,2,6,6-Tetramethyl-4-(1',3'-dioxopentyloxy)-piperidin
• 1-{2"-[N-n-Butyl-N-(1',3'-dioxobutyl)]-amino-2"- methyläthyl}-2,2,6,6-tetramethyl-4-heptanoyloxy-piperidin
• 1-[(2'-Phenyl-3',6'-dioxa-5'-methyl-7',9'-dioxo)-decyl]-2,2,6,6-tetramethyl-piperidin
• N,N-Dimethyl-N,N'-bis-[1-(3'-oxa-4',6'-dioxo)-heptyl-2,2,6,6-tetramethyl-piperidin-4-yl]-hexamethylendiamin
• Bis-[1-(3'-oxa-4',6'-dioxo)-heptyl-2,2,6,6-tetramethyl-piperidin-4-yl]-p-xyliden
• Bis-[1-(3'-oxa-4',6'-dioxo)-heptyl-2,2,6,6-tetramethyl-piperidin-4-yl]-adipat
• Bis-[1-(3'-oxa-4',6'-dioxo)-heptyl-2,2,6,6-tetramethyl-piperidin-4-yl]-n-butyl-malonat
• Bis-[1-(3'-oxa-4',6'-dioxo)-heptyl-2,2,6,6-tetramethyl-piperidin-4-yl]-methyl-carbäthoxymethyl-malonat
• 3-n-Octyl-7,7,9,9-tetramethyl-8-[(3'-oxa-4',6'-dioxo)-heptyl]-1,3,8-triazaspiro-[4,5]-decan-2,4-dion
• 1,2,2,6,6-Pentamethyl-4-[1',4',8'-trioxa-9',11'-dioxo-6'-(1",3"-dioxobutyloxy)]-piperidin
• 2,2,6,6-Tetramethyl-4-[4'-(1",3"-dioxobutyloxy)-3'-t.butyl-phenyl]-piperidin
• 2,2,6,6-Tetramethyl-4-[3',5'-dimethyl-4'-(1",3"- dioxo-butyloxy)-cyclohexyl]-piperidin
• 3-Aethyl-3-(1',3'-dioxo-butyloxy-methyl)-8,8, 10,10-tetramethyl-1,5-dioxa-9-aza-spiro[5,5]-undecan
• 3-(2'-Methyl-3'-oxa-4',6'-dioxo-heptyl)-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]-decan-2,4-dion
• Bis-(2,2,6,6-tetramethyl-piperidin-4-yl)-[2'-methoxymethyl-3'-oxa-4',6'-dioxo-heptyl]-malonat
• Bis-(2,2,6,6-tetramethyl-piperidin-4-yl)-methyl-[N-benzyl-N-(1',3'-dioxo-butyl)-aminopropyl]-malonat
• 2,2,6,6-Tetramethyl-4-cyano-4-(1',3'-dioxo- butyloxy)-piperidin.

Examples of compounds of the formula I are metal complexes of a metal M ^q ⊕ with one of the following ligands:

• 2,3,6-trimethyl-2,6-diethyl-4- (1 ', 3'-dioxobutyloxy) piperidine
• 2,2,6,6-tetramethyl-4- (1 ', 3'-dioxopentyloxy) piperidine
• 1- {2 "- [Nn-Butyl-N- (1 ', 3'-dioxobutyl)] - amino-2" - methylethyl} -2,2,6,6-tetramethyl-4-heptanoyloxy-piperidine
• 1 - [(2'-Phenyl-3 ', 6'-dioxa-5'-methyl-7', 9'-dioxo) decyl] -2,2,6,6-tetramethyl-piperidine
• N, N-Dimethyl-N, N'-bis- [1- (3'-oxa-4 ', 6'-dioxo) -heptyl-2,2,6,6-tetramethyl-piperidin-4-yl] - hexamethylene diamine
• Bis- [1- (3'-oxa-4 ', 6'-dioxo) heptyl-2,2,6,6-tetramethyl-piperidin-4-yl] p-xylidene
• Bis- [1- (3'-oxa-4 ', 6'-dioxo) heptyl-2,2,6,6-tetramethyl-piperidin-4-yl] adipate
• Bis- [1- (3'-oxa-4 ', 6'-dioxo) heptyl-2,2,6,6-tetramethyl-piperidin-4-yl] n-butyl malonate
• Bis- [1- (3'-oxa-4 ', 6'-dioxo) heptyl-2,2,6,6-tetramethyl-piperidin-4-yl] methyl carbäthoxymethyl malonate
• 3-n-octyl-7,7,9,9-tetramethyl-8 - [(3'-oxa-4 ', 6'-dioxo) heptyl] -1,3,8-triazaspiro- [4,5] -decane-2,4-dione
• 1,2,2,6,6-pentamethyl-4- [1 ', 4', 8'-trioxa-9 ', 11'-dioxo-6' - (1 ", 3" -dioxobutyloxy)] - piperidine
• 2,2,6,6-tetramethyl-4- [4 '- (1 ", 3" -dioxobutyloxy) -3'-t.butylphenyl] piperidine
• 2,2,6,6-tetramethyl-4- [3 ', 5'-dimethyl-4' - (1 ", 3" - dioxo-butyloxy) cyclohexyl] piperidine
• 3-ethyl-3- (1 ', 3'-dioxo-butyloxy-methyl) -8.8, 10,10-tetramethyl-1,5-dioxa-9-aza-spiro [5,5] -undecane
• 3- (2'-Methyl-3'-oxa-4 ', 6'-dioxo-heptyl) -7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decan-2 , 4-dione
• Bis- (2,2,6,6-tetramethyl-piperidin-4-yl) - [2'-methoxymethyl-3'-oxa-4 ', 6'-dioxo-heptyl] malonate
• Bis- (2,2,6,6-tetramethyl-piperidin-4-yl) methyl- [N -benzyl-N- (1 ', 3'-dioxobutyl) aminopropyl] malonate
• 2,2,6,6-tetramethyl-4-cyano-4- (1 ', 3'-dioxobutyloxy) piperidine.

The ligands listed here can be converted into metal complexes with a metal M ^q ⊕ by one of the processes described below.

The compounds according to the invention are distinguished in that the ligams L complexed therein contain at least one radical R ₆ with the meaning described above. The ligands of the formula II used for the synthesis are new, with the exception of the acetoacetic (2,2,6,6-tetramethyl-4-piperidinyl) ester, which also falls under the general formula II, and are therefore also new The ligands of the formula II can be prepared in a known manner from the analogous compounds of the formula II ', in which the substituent R ₆ in the radicals Z ₁ and Z _{2 is} replaced by hydrogen, and all other symbols in the formula II have the meaning given, are produced. In particular, the procedure is such that the corresponding hydroxy or amino derivatives are reacted directly or in a solvent with a decetene corresponding to formula V or a diketene homolog, with the addition of a catalyst usually not being necessary (cf. Houben-Weyl "Methods of Organic Chemistry" 4th edition, volume 7 / 4 page 226ff). The diketene is preferably used in a stoichiometrically equivalent amount or in a 10 to 10% excess. Particularly suitable solvents for these reactions are benzene, toluene, dioxane, dichloroethane, pyridine or dimethylformamide. On the other hand, these compounds can, however, be obtained in a manner known per se from the intermediates of the formula II 'and β-ketocarboxylic acid esters described by the above definition.

Those intermediates (of the general formula II ') in which geminal hydroxyl groups occur can be derived from 2,2,6,6-tetraalkylpiperidine derivatives which contain primary or secondary amino groups or primary hydroxyl groups and 2,3-epoxy-1-propanol according to the known methods of epoxy reactions can be obtained.

The starting materials of the formula II 'are known or, if they are new, can be prepared by methods known per se and in analogy to known compounds. For example, 4-aminopiperidine derivatives are important starting products which can be prepared by the processes described in DT-OS 2 040 975 or DT-OS 2 349 962. Those piperidine derivatives which are substituted on the 4-amino group by an alkylamino group can be prepared in an analogous manner by starting from a piperidin-4-one derivative and reacting it with a monoalkylated diamine.

The piperidine derivatives, which contain an alkoxyamino group in the 4-position (in particular the oxypropylamino group), are prepared from the corresponding 4-hydroxypiperidi derivatives, which are added to acrylonitrile by methods known per se, and the cyano group is then hydrogenated to the corresponding primary amine. Other important starting products for the preparation of compounds of the formula I are those compounds which, in the 4-position of the piperidine ring, carry both a cyano and a hydroxyl group (cyanohydrins) or at the same time a cyano group and an amino group. Your manufacture will in U.S. Patent 3,513,170. The corresponding 4-methylamino derivatives are then obtained in a known manner by hydrogenation of these nitriles. a-Aminocarboxylic acid esters, the α-carbon atom of which is in the 4-position in the piperidine derivatives in question, are also starting products for the preparation of claimed compounds of the formula I.

The free acids can be derived from the corresponding piperidin-4-one derivatives by the method of H.T. Bucherer (J. Prakt. Chem. 140, 291 (1934)) can be prepared via hydantoins as intermediates and subsequent alkaline saponification. The conversion into the corresponding esters takes place in a manner known per se with the aid of an acid catalyst.

The piperidin-4-one derivatives substituted on the nitrogen in the 1-position can, as described in British Patent 1,337,600, be obtained by protecting the keto group by converting it to a ketal. After the introduction of the substituent in the 1-position by the usual methods, the protective group is split off again in a known manner.

The metal complexes of the compounds of the formula I are prepared in a manner known per se, for example by dissolving the .beta.-keto esters or .beta.-ketoamides of the formula II in a non-aqueous solvent, preferably a lower alcohol (in particular ethanol) an amount of an alkali alcoholate equivalent to the enolizable keto groups can be added. So many moles of a dissolved metal salt are slowly added that the molar ratio between the metal ion the valence q +. and the neutralized enolate groups of the ligand molecule r / q. Above all, the solvent used for the metal salt is that which was initially used or which can be mixed with it. The reaction mixture is then stirred at a temperature between 30-100 ° C for about 1 hour. Preferred metal salts are those whose anions result in poorly soluble precipitates with the alkali ions in the selected solvents. This usually takes place at the. Add the metal salt or when stirring or heating the reaction mixture. In these cases, the alkali salts can be separated off by filtration. Otherwise, they can often be separated after evaporation of the solvent or by extraction of the metal compound with a non-polar solvent. - Suitable metal salts are, in particular _, chlorides, such as nickel chloride, cobalt (II) chloride or dibutyltin dichloride. If non-anhydrous salts are used or if the solvents used contain water, this can be incorporated into the complex forming itself as such or in deprotonated form as hydroxyl ion. In these cases, the end products often still contain the alkali metal that was used as the alcoholate to form the enolate groups. If a salt of a carboxylic acid is used as the metal salt (for example the nickel salt of 2-ethylcaproic acid), the carboxylate ion can often not be separated off or only partially as an alkali metal salt because it is incorporated into the complex as a further ligand anion in addition to the enolate ions.

Instead of inorganic metal salts and metal carboxylates, metal alkoxides (such as aluminum triisopropylate) can also be used as reaction components for the formation of metal complexes of the compound of formula I. In these cases, the neutralization of the β-keto ester or β-ketoamide with an alkali alcoholate is dispensed with.

If the metal complexes of the compounds of the formula I contain an amine as a further ligand, this can be added before the addition of the alkali alcohol or the metal complex obtained in the manner described above can be dissolved in a solvent containing the amine and then removed again by evaporation .

If one proceeds in the manner described in the preparation of metal complexes of the compounds of the formula I, mixtures of various complexes often arise, especially those in which the ratio of the metal ion to the ligand L is greater than r / q. Like the uniform compounds of this formula, they can be used as effective stabilizers.

The. Compounds of formula 1 can be used according to the present invention as stabilizers for plastics against their damage by the action of oxygen, heat and light. Examples of such plastics are the polymers listed in DT-OS 2 456 864 on pages 12-14.

Of particular importance is the stabilization of polyolefins, styrene polymers, polyamides and polyurethanes, for which the compounds of the formula I are outstandingly suitable. Examples of these are high and low density polyethylene, polypropylene, ethylene-propylene copolymers, polystyrene, styrene-butadiene-acrylonitrile tercopolymers, mixtures of polyolefins or of styrene polymers, polyurethanes based on polyether or polyester in the form of lacquers, threads, films, elastomers or foams.

The stabilizers are added to the plastics in a concentration of 0.01 to 5% by weight, calculated on the material to be stabilized. Preferably 0.03 to 1.5, particularly preferably 0.15 to 0.6% by weight of the compounds, calculated on the material to be stabilized, are incorporated into the latter.

The incorporation can take place after the polymerization, for example by mixing the compounds and, if appropriate, further additives into the melt according to the methods customary in industry, before or during shaping, or also by applying the dissolved or dispersed compounds to the polymer, optionally with subsequent addition Evaporation of the solvent.

The new compounds can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example in a concentration of 2.5 to 25% by weight.

In the case of cross-linked polyethylene, the compounds are added before cross-linking.

The invention therefore also relates to the plastics stabilized by the addition of 0.01 to 5% by weight of a compound of the formula I, which may also contain other known and customary additives. The plastics stabilized in this way can be used in various forms, e.g. as foils, fibers, tapes, profiles or as binders for paints, adhesives or putties.

• Antioxydantien, wie einfache 2,6-Dialkylphenole, Derivate von'alkylierten Hydrochinonen, hydroxylierte Thiodiphenyläther, Alkyliden-bisphenole, 0-, N- und S-Benzylverbindungen, hydroxybenzylierte Malonester, Hydroxybenzyl-Aromaten, s-Triazinverbindungen, Amide der β-(3,5-Di-tert.-butyl-4-hydroxyphenyl)-propionsäure, Ester der β-(3,5-Di- tert.-butyl-4-hydroxyphenyl)-propionsäure, Ester der β-(5-tert.-Butyl-4-hydroxy-3-methylphenyl)-propionsäure, Ester der 3,5-Di-tert.-butyl-4-hydroxyphenylessigsäure, Acylaminophenole, Benzylphosphonate, Aminoarylderivate, UV-Absorber und Lichtschutzmittel, wie 2-(2'-Hydroxyphenyl)-benztriazole, 2,4-Bis-(2'-hydroxyphenyl)-6-alkyl-s-triazine, 2-Hydroxybenzophenone, 1,3-Bis-(2'-hydroxybenzoyl)-benzole, Ester von gegebenenfalls substituierten Benzoesäuren, Acrylate, des weiteren Nickelverbindungen, sterisch gehinderte Amine, Oxalsäurediamide, Metalldesaktivatoren, Phosphite, peroxidzerstörende Verbindungen, Polyamidstabilisatoren, basische Co-Stabilisatoren, PVC-Stabilisatoren, Nukleierungsmittel oder sonstige Zusätze wie z.B. Weichmacher, Gleitmittel, Emulgatoren, Füllstoffe, Russ, Asbest, Kaolin, Talk, Glasfasern, Pigmente, optische Aufheller, Flammschutzmittel, Antistatica.

Examples of further additives with which the stabilizers which can be used according to the invention can be used are:

• Antioxidants such as simple 2,6-dialkylphenols, derivatives of alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, 0-, N- and S-benzyl compounds, hydroxybenzylated malonic esters, hydroxybenzyl aromatics, s-triazine compounds, amides of the β- (3rd , 5-Di-tert-butyl-4-hydroxyphenyl) propionic acid, esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, esters of β- (5-tert.- Butyl-4-hydroxy-3-methylphenyl) propionic acid, esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, acylaminophenols, benzylphosphonates, aminoaryl derivatives, UV absorbers and light stabilizers, such as 2- (2'-hydroxyphenyl ) -benztriazoles, 2,4-bis (2'-hydroxyphenyl) -6-alkyl-s-triazines, 2-hydroxybenzophenones, 1,3-bis (2'-hydroxybenzoyl) benzenes, esters of optionally substituted benzoic acids, Acrylates, furthermore nickel compounds, sterically hindered amines, oxalic acid diamides, metal deactivators, phosphites, peroxide-destroying compounds, polyamide stabilizers, basic co-stabilizers , PVC stabilizers, nucleating agents or other additives such as plasticizers, lubricants, emulsifiers, fillers, carbon black, asbestos, kaolin, talc, glass fibers, pigments, optical brighteners, flame retardants, antistatic agents.

Examples of further additives with which the stabilizers which can be used according to the invention can be used can be found in DT-OS 2 427 853 on pages 18-24.

The preparation and use of the compounds according to the invention is described in more detail in the following examples. The temperature information always relates to ° C.

Examples 1 to 10

The compounds of Examples 1-10 were prepared according to the following general procedure (see Table 1)

0.1 mole of the compounds mentioned in column 2 were dissolved in 100 ml of benzene and the amount of diketene (β-methylene-β-propiolactone) mentioned in column 3, which was mixed with benzene in a ratio of 1: 1, within 30 Dripped minutes. The temperature of the reaction mixture was not above 60 °. The mixture was then heated to 60 ° for 4 hours and the solvent was then evaporated off. The residue was worked up by the method described in column 4. The end product mentioned in column 5 showed the properties mentioned in column 6.

Examples 17-26

The compounds of Examples 17-26 (see Table 2) were prepared according to the following general procedure.

0.1 mole of the compounds designated in column 2 were dissolved in 200 ml of methanol and 100 ml of a 1.0 molar methanolic sodium methylate solution were added. 0.05 mol of the metal salts referred to in column 3, dissolved in 160 ml of methanol, were added dropwise to these solutions in the course of 30 minutes. The reaction mixture was then heated under reflux for 30 minutes and the neutral salt which had precipitated out was separated off by filtration. In Example 14, the reaction mixture was not heated after addition of the metal salt, with no neutral salt separating out. The solutions obtained were evaporated to dryness and the residue was eluted with the extractant designated in column 4. The extract was evaporated and dried at a temperature of 60 ° (exception example 14: 40 °) and a pressure of 11 mm Hg for 10 hours. In this way, the solid end products designated in column 5 were obtained, the properties of which are mentioned in column 6.

Example 27

18; 5 g (0.05 mol) of 1- [2 '- (1 ", 3" -dioxobutyloxy) ethyl] -4- (1 ", 3" -dioxobutyloxy) -2,2,6,6-tetramethylpiperidine were dissolved in 200 ml of methanol and 5.40 g (0.1 mol) of sodium methylate was added.

To this solution was added dropwise in the course of 30 minutes 16.3 g (0.05 mol) in 330 ml of benzene dissolved nickel (II) enanthate (per mole of ^1/2 mole of water) a. The mixture was stirred at room temperature for 4 hours, clarified by filtration and evaporated to dryness. The residue was washed with water and dried at a temperature of 60 ° and a pressure of 11 mm Hg for 18 hours. In this way, the 1: 1 nickel (II) complex of 1- [2 '- (1 ", 3" -dioxobutyloxy) -ethyl] -4- (1 ", 3" -doxobutyl-oxy) - was obtained. 2,2,6,6-tetramethylpiperidi.n dienolate as a monohydrate in the form of a yellow-green powder.

Elemental analysis:

found C51.40% H 7.22% N 2.92% Ni 13.0%
calc. for monohydrate 51.37% 7.02% 3.15% 13.2%.

Example 28

25.3 g (0.05 mol) of N, N'-bis- (1 ', 3'-dioxobutyl) -N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) - Ethylenediamine was dissolved in 500 ml of toluene and 76.9 ml of a 1.3 molar sodium methylate solution (0.1 mol) were added. Under reflux, 16.3 g (0.05 mol) dissolved nickel (II) enanthate have now been in 330 ml of toluene (per mole of ^1/2 mole of water) was added dropwise and the reaction mixture is boiled for 15 minutes under reflux. The sodium oenanthate which separated out was filtered off and the filtrate was evaporated to dryness. The residue was extracted at room temperature with toluene, evaporated in vacuo and dried at a temperature of 60 ° and a pressure of 11 mm Hg for 10 hours. The 1: 1 nickel complex of N, N'-bis (1 ', 3'-dioxobutyl) -N, N'-bis- (2,2,6,6-tetramethyl- 4-piperidyl) -ethylenediamine-dienol as a light green powder which contains 9.4% nickel and 9.2% nitrogen and in which, in addition to the ligand mentioned, oenanthic acid anions are coordinated.

Example 29

. 12.1 g (0.05 mol) of 2,2,6,6-tetramethyl-4- (1 ', 3'-dioxobutyloxy) piperidine were dissolved in 400 ml of ethanol and 3.40 g (0.0166 Mol) aluminum isopropylate added. When the mixture is heated, a clear solution is obtained which is heated under reflux for two hours. Then the solvent and the liberated isopropanol are evaporated off and the product is dried at a temperature of 60 ° C. and a pressure of 11 mmHg. In this way, the 1: 3 aluminum (II) complex of 2,2,6,6-tetramethyl-4- (1 ', 3'-dioxobutyloxy) piperidine enolate is obtained as a white powder.

Elemental analysis

• found C 62.33% H 9.03% N 5.64% Al 3.73%
• calc. C 62.63% H 8.89% N 5.62% Al 3.61%

Example 30 Sun protection effect in PP fibers

1000 parts of unstabilized polypropylene powder (melt index ~ 18) are mixed in a drum mixer with 1 part of pentaerithrytyl tetrakis [3- (3.5-di-tert-butyl-4-hydroxylphenyl) propionate] and with 3 parts of the additives listed in the table and then extruded and granulated in an extruder at 220 ° C. The granules obtained are spun into a 130/37 denier multifilament in a laboratory melt spinning plant at a maximum temperature of 270 ° C. and a speed of 300 m / minute. This is drawn and twisted using a draw twisting machine. The draw ratio is 1: 5.6 and the thread count is 15 / meter, so that multifilaments 130/37 denier are finally obtained. These multifilaments are mounted on white cardboard and exposed in the Xenotest 1200,

The exposure time up to 50% loss of tensile strength is the measure of the protective effect.

The results are summarized in Table 3.

Example 31 Sun protection effect in high pressure polyethylene foils

100 parts of low-density polyethylene granules (= 0.917) are homogenized with 0.05 parts of a stabilizer from the following table in a Brabender plastograph at 180 ° C. for 10 minutes. The mass obtained in this way is removed from the kneader as quickly as possible and pressed into a 2-3 mm thick plate in a toggle press. Part of the raw compact obtained is cut out and pressed between two high-gloss hard aluminum foils with a hand-hydraulic laboratory press for 6 minutes at 170 ° and 12 tons pressure to a 0.1 mm thick foil, which is immediately quenched in cold water. Sections of 60 x 44 mm are now punched from this and exposed in the Xenotest 1200. These test specimens are removed from the exposure apparatus at regular intervals and checked for their carbonyl content in an IR spectrophotometer. The increase in carbonate absorbance upon exposure is a measure of the photooxidative degradation of the polymer (see L. Blaban et al., _J. Polymer Sei. Part C, 22, 1059-1071 (1969); JF Heacock, J. Polymon dei Part.A-1, 22, 2921-34 (1969); DJ Carlsson and DM. Wil.es, Macromolecules 2, 587-606 (1969) and is associated with a decrease in the mechanical properties of the polymer.

The measure of the protective effect is the time until a carbonyl extinction of 0.100 is reached.

The results are summarized in Table 4.

Example 32 Sun protection of polyethylene blown films

100 parts of low-density polyethylene (melt index 0.1-0.3 g / 10 min., 190 ° C, 2.15 kg) were 2 minutes in a cooled intensive mixer from Henschel with one of the additives listed in Table 1 and 0.03 part of 3 (3 ', 5'-di-tert-butyl 4'hydroxyphenyl) octadecylpropionate mixed, extruded from a single-screw extruder with a diameter of 35 mm and a length of 700 mm, the temperature in the first section at 190 ° C. and in the following three at 200 ° C was placed, cooled in water and granulated. These granules were pressed at 190 ° C. through a blown film extrudar with a diameter of 60 mm and a length of 1200 mm. At the exit of the extruder there was an annular die with a 120 mm diameter, which was set to 200 ° C. The tube ring-ejected film was inflated in a ratio of 1: 1.3. The take-off speed was 5 m / minute. The foils were 0.2 mm thick.

These films were exposed in the Xenotest exposure device 1200.

, Als Mass der Stabilisierung wird in der nachfolgendan Tabelle die Belichtungszeit angegeben, welehe die Folie erträgt, bis sie die erwähnte Carbonyloxtinktion von

erreicht.

The carbonyl absorbance of the films was measured at regular intervals in an infrared spextrophotometer. The oxidation indicated by the carbonyl absorbance corresponds to a mechanical damage to the film in the range of 0.1, which indicates the beginning of the uselessness

As a measure of stabilization, the exposure time is given in the table below, which the film can endure until it has the aforementioned carbonyl oxy-absorbance of

reached.

Example 33 Stabilization of polypropylene against light

100 parts of polypropylene powder (Moplen, Fiber grade, from Montedison) are mixed with 0.2 parts of octadecyl β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.25 part of a stabilizer in the following table 1 homogenized in Brabender plastograph at 200 ° C for 10 minutes. The mass obtained in this way is removed from the kneader as quickly as possible and pressed into a 2-3 mm thick plate in a toggle press. Part of the compact obtained is cut out and pressed between two high-gloss hard aluminum foils with a hand-hydraulic laboratory press for 6 minutes at 260 ° C and 12 tons pressure to a 0.1 mm thick foil, which is immediately quenched in cold water. Sections of 60 x 44 mm are punched out of this and exposed in the Xenotest 150. These test specimens are removed from the exposure apparatus at regular intervals and checked for their carbonyl content in an IR spectrophotometer. The increase in carbonyl absorbance at 5.85 μ during the exposure is a measure of the photooxidative degradation of the polymer (see L. Blaban et al., J. Polymer Sci, Part C; 22, 1059-1071 (1969) and is based on experience associated with a decrease in the mechanical properties of the polymer The measure of the protective effect is the time until a carbonyl extinction of approximately 0.3 is reached, at which the comparison film is brittle.

The protective effect of the stabilizers according to the invention can be seen from the following Table 1:

Polypropylene ribbon

100 parts of polypropylene powder (melt index 1.5 g / 10 minutes, 230 ° C., 2160 g) were mixed in a drum mixer with 0.1 part of pentacrythritol tetrakis [3- (3 ', 5'-di-tertiary-butyl-4-hydroxyphenyl) propionate ) and 0.15 parts of the additives listed in the table below are mixed and extruded in an extruder at 200 to 220 ° C. and granulated. The granules obtained were processed in a conventional manner by means of an extruder with a slot die to form films which were cut into strips which were then stretched to six times their length at elevated temperature. The titer of these tapes is 700 - 900 den, their width 4 mm, their tensile strength 5.5-6.5 g / den. These ribbons were exposed in a Xenotest 1200. Samples were subjected to a tensile strain test at regular intervals, with a progressive decrease in the tensile strength with increasing exposure. The exposure time until the tear strength drops to half the initial value is extended by the action of the light stabilizers.

Claims (5)

1. New compounds of the general formula I

wherein M ^{q⊕ is} a double or triple positively charged metal ion, and q is 2 or 3, and r is 1 or 2, the quotient q / r being 1, 1.5, 2 or 3, and L is a piperidine which is substituted by at least one enolate group in the 1- or 4-position and whose ring nitrogen is sterically hindered by alkyl substituents at the adjacent positions, and m is 0, 1 or 2, and ^{A is} H ₂ 0 or an amine. 2. New compounds according to claim 1 of formula I wherein M ^{q⊕ is} a double or triple positively charged metal ion, and q is 2 or 3, and r is 1 or 2, the quotient q / r being 1, 1.5, 2 or 3, and L is a group of formula II

is what R _{1 is} hydrogen or C ₁ -C ₄ alkyl, and Z _{1 is} hydrogen, C ₁ -C ₁₂ alkyl, _C3 - _C8 alkenyl, ^C ₃ - ^C ₄ alkynyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₈ aralkyl, an aliphatic acyl group with 1-4 C atoms, or one the groups -CH ₂ COOR ₂ or -CH ₂ -CH (R ₃ ) -OR ₄ , or a radical - (CH ₂ ) ₄ -R ₅ , -CH ₂ -CH = CH-CH ₂ -R ₅ ,

or a group of formula III

means where R _{2 is} C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl, and R _{3 is} hydrogen, methyl or phenyl, and ^R _{4 represents} an aliphatic C ₁ -C ₁₈ acyl group, an aromatic C ₇ acyl group, an araliphatic C ₈ -C ₉ acyl group or an alicyclic C ₆ -C ₉ acyl group, the aromatic part optionally containing chlorine, C ₁ -C ₄ alkyl , C ₁ -C ₈ alkoxy, and / or hydroxy may be substituted, and R _{5 is} a group of formula IV

means, wherein R ₁ , Z ₂ and Z _{3 have} the meaning given here, and R _{6 is} a group of formula V.

is what R _{9 is} hydrogen or C ₁ -C ₄ alkyl, and R ₇ and R _{8 are,} independently of one another, hydrogen, methyl, phenyl, C ₂ -C ₉ alkoxymethyl or a radical - ^CH ₂ - ^0-R ₆ , in which R ₆ has the meaning defined above, and a 0, 1 or 2, and b is 0 or 1, and c is 0 or, if a and / or b are different from 0, is also 1, and X and Y independently of one another -0- or -NR ₁₀ , wherein R _{10 is} hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₈ alkenyl, cyclo hexyl, C ₃ -C ₂₁ alkoxyalkyl, C ₇ -C ₁₃ aralkyl, phenyl optionally substituted by C ₁ -C ₈ alkyl and / or C ₇ -C ₈ alkoxy or a group -CH ₂ -CH ₂ -OR ₆ , in which R _{6 has} the meaning given above, and R _{10 is} also a group of the formula IV

wherein R _{1 has} the meaning given above, and R _{11 is} hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₈ alkenyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₈ aralkyl, an aliphatic acyl group with 1-4 C atoms or a group -CH ₂ COOR ₂ , in which R _{2 has} the meaning defined above, means, and Z _{2 is} hydrogen, C ₂ -C ₁₈ aliphatic acyloxy, optionally substituted by C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy benzoyloxy or an optionally C ₁ -C ₈ N-alkyl substituted C ₂ -C ₁₈ acylamido group , or one of the groups -R ₁₂ , - (CH ₂ ) _d -R ₁₂ ,

wherein d is 2 to 10 and R _{12 is} a group of formula VII

is what R ₁ and Z _{1 have} the meaning given above, or Z ₂ also a group of formula VIII

represents what R _{12 has} the meaning given above, and X 'is -0- or -NR ₁₄ , where R _{14 is} hydrogen or C ₁ -C ₄ alkyl, and R ₁₃ - (CH ₂ ) _e - or a group

is, where e is 0 to 8, and R _{15 and} r ₁₆ independently of one another are hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₈ alkenyl, C ₇ -C ₁₁ aralkyl, cyanomethyl, cyanoethyl or a group -CH ₂ COOR ₁₇ , where R _{17 is} methyl or ethyl, or Z ₂ one of the groups

is where a, b, c, X, Y, R ₆ , R7 and R _{8 have} the meaning given above, and f, a'undb 'are 0 or 1, and g is 0 or, if a 'and / or b' are different from 0, is also 1, and. R _{22 and} R ₂₃ independently of one another are hydrogen, C ₁ -C ₄ alkyl, cyclohexyl, phenyl, benzyl, α-methylbenzyl or α, α-dimethylbenzyl, and. Z _{3 is} hydrogen or cyano, or Z ₂ and Z ₃ together one of the groups XV, XVI or XVII

wherein R ₆ , R ₇ and R _{12 have} the meaning given above and ^R _{18 is} hydrogen, C ₁ -C ₈ alkyl, allyl, phenyl or benzyl, and R _{19 is} hydrogen, C ₁ -C ₈ alkyl, allyl or benzyl, and R _{20 is} C ₁ -C ₄ alkyl or a group of formula V with the meaning given above and R _{21 is} C ₂ -C ₆ alkylene, cyclohexylidene, phenylene, diphenylene, 4,4'-diphenylene oxide or 4,4'-diphenylene methane, or Z ₂ also a group of the formulas XII, XIII or XIV R _{29 represents} hydrogen or alkyl. 3. Compounds according to claim 1 of formula I, wherein 2+ 2+ 2+ 2+ 2+ 2+ 3+ 2+ M ^q⊕ Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Cr ³⁺ , Co ²⁺ , Ni ²⁺ , Vo ²⁺ , Mo0 ²⁺ , (R *) ₂ Sn ²⁺ or (CH ₂ CH ₂ COOR *) ₂ Sn ²⁺ means, in which R * is C ₁ -C ₈ alkyl, and q is 2 or 3, and r is 1 or 2, the quotient q / r being 1, 1.5, 2 or 3, and L is a group of formula II, wherein R _{1 is} hydrogen or methyl, and Z _{1 is} hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₄ alkenyl, C ₃ alkynyl, C ₂ -C ₁₀ alkoxyalkyl, C ₇ -C ₈ aralkyl, acetyl or one of the groups -CH ₂ COOR ₂ or -CH ₂ -CH (R ₃ ) -OR ₄ , or a radical - (CH ₂ ) ₄ -R ₅ ,

or a group of the formula III, where ^R _{2 is} C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl, and R _{3 is} hydrogen or methyl, R _{4 is} an aliphatic acyl group with 1-12 C atoms, and R _{5 is} a group of formula IV in which Z ₂ and Z _{3 have} the meaning given below and R _{1 is} hydrogen, and R _{6 represents} a group of formula V, wherein R _{9 is} hydrogen or methyl, and R ₇ and R _{8 are} independently hydrogen or methyl, and a 0, 1 or 2, and

mean what R ₆ has the meaning given above, and R _{24 is} hydrogen, methyl or ethyl, and R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, cyclohexyl, C ₇ -C ₈ aralkyl or a group -CH ₂ -COOR2 ₆ or -CH ₂ -CH (R ₈ ) -OR ₆ , in which R _{26 is} C ₁ -C ₁₈ alkyl, and R ₆ and R _{8 have} the meaning given above, and m is 0, 1 or 2, and AH ₂ O or an amine of the formula (XVIII)

is what R _{27 is} optionally substituted alkyl, cycloalkyl, aryl, aralkyl, an optionally substituted aminoalkyl or piperidinyl group, and R _{28 is} hydrogen or optionally substituted alkyl, cycloalkyl, an optionally substituted aminoalkyl group or a piperidinyl group .pe, or R ₂₇ and R ₂₈ together with the N atom are an alkyl group-substituted or unsubstituted pyrrolidine; Form piperidine or morpholine ring, and wherein R ₆ and R _{7 have} the meaning given above, and R _{18 represents} hydrogen, _{R19 is} hydrogen, C ₁ -C ₄ alkyl, allyl or benzyl, R _{20 is} C ₁ -C ₄ alkyl or a group of formula V with the meaning given above, and R _{21 is} C ₂ -C ₆ alkylene, cyclohexylidene or phenylene or Z ₂ also a group of formula XIIa

is what a, b, c, R ₆ and R7 have the meaning given above, and f 0 or. Is 1, and X ₁ -0- or

means what

Hydrogen, C ₁ -C ₁₂ alkyl, cyclohexyl, C ₃ -C ₁₄ alkoxyalkyl, C ₇ -C ₈ aralkyl, optionally mono- or disubstituted phenyl with C ₁ -C ₃ alkyl and / or C ₁ -C ₈ alkoxy or if a , b and c 1, R _{7 are} hydrogen and Y is -0-, also a group -CH ₂ -CH ₂ -OR ₆ , in which R _{S has} the meaning given above, and

furthermore means a group VI, wherein R _{1 has} the meaning given above, and R _{11 is} hydrogen, methyl or allyl, and Y ₁ -0- or

means what

Is hydrogen, C ₁ -C ₈ alkyl or phenyl, or Z _{2 is} also one of groups XIII or XIV, wherein R _{6 has} the meaning given above, and R ₂₂ and R _{23 are} independently hydrogen, methyl or ethyl, and Z _{3 is} hydrogen or cyano, or b 0 or 1, and c is 0 and, if a and / or b are different from 0, is also 1, and X is -O-, and - ₀ - or - _N - _R10 , where R _{10 is} hydrogen or methyl, or if a, b and c 1, R _{7 are} hydrogen and Y is -0-, also a group ^p e -CH ₂ -CH _Z -OR ₆ , where R _{6 has} the meaning given above, means, and Z ₂ 'is hydrogen, C ₂ -C ₁₂ aliphatic acyloxy, optionally benzoyloxy mono- or disubstituted with methyl or methoxy, or an optionally C ₁ -C ₄ N-alkyl-substituted C ₂ -C ₁₂ acylamido group, or one of the groups -R ₁₂ ,

or

where d is 2 to 6, and R _{12 is} a group of the formula VII, in which R ₁ and Z ₁ have the meaning given above, or Z ₂ also denotes a group of the formula VIII, in which X 'is -0- or -NR ₁₄ , where ^R _{14 is} hydrogen or C ₁ -C ₄ alkyl, and ^R ₁₃ - ( ^C H ₂ ) _e - or a group

is where e is 0 to 8, and R ₁₅ and R ₁₆ independently of one another hydrogen, C ₁ -C ₄ alkyl, allyl, benzyl, cyanomethyl, cyanoethyl or a group -CH ₂ COOR ₁₇ , where R _{17 is} methyl or ethyl, mean _or Z _{2 is} a group of the formulas IX, X or XI, r is 1 or 2, the quotient..q / r being 1, 1..5, 2 or 3, and L is a group of formula II, wherein R _{1 is} hydrogen or methyl, and Z _{1 is} hydrogen, C ₁ -C ₄ alkyl, allyl, C ₂ -C ₆ alkoxyalkyl, benzyl, acetyl or one of the groups -CH ₂ COOR ₂ or -CH ₂ -CH (R ₃ ) -OR ₄ or a group of the formula III means where R _{2 is} C ₁ -C ₄ alkyl, and R _{3 is} hydrogen, and R4 is an aliphatic acyl group with 1-8 C atoms, and R _{6 represents} a group of formula V, wherein R _{9 is} hydrogen, and R _{7 is} hydrogen, and R _{8 represents} hydrogen or methyl, and a is 0, 1 or 2, and b is 0 or 1, and c is 0 or, if a and / or b are different from 0, is also 1, and X is -0-, and Y -0- or

R ₁₀ means, wherein R _{10 is} hydrogen or methyl, or, if a, b and c 1 and Y are -0-, also a group -CH ₂ -CH ₂ -OR ₆ , in which R _{6 has} the meaning given above, and Z _{2 is} hydrogen, C ₂ -C ₇ aliphatic acyloxy, optionally benzoyloxy monosubstituted with methyl or methoxy, or a C ₂ -C ₇ acylamido group optionally substituted with methyl N or one of the groups - (CH ₂ ) _d -R ₁₂ ,

is Z ₂ and Z ₃ together mean one of the formulas XV, XVI or XVII, in which R _{6 has} the meaning given above, and R _{24 is} hydrogen, methyl or ethyl and R _{25 is} hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₈ alkenyl, a group -CH ₂ COOR ₂₆ or -CH ₂ -CH (R ₈ ) -OR ₆ , where R ₆ and R _{8 have} the meaning given above have and R _{26 is} C ₁ -C ₁₂ alkyl, and m is 0, 1 or 2, and AH ₂ O or an amine of formula XVIII, wherein R ₂₇ C ₁ -C ₁₈ alkyl optionally substituted with -OH, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₁₀ aryl optionally substituted with C ₁ -C ₁₂ alkyl, C ₇ -C ₂₀ aralkyl, an optionally substituted aminoalkyl group with 1 Is -8 carbon atoms in the alkyl part or piperidinyl group, and R _{28 denotes} hydrogen, or C ₁ -C ₁₈ alkyl optionally substituted with -OH, C ₅ -C ₁₂ cycloalkyl or an optionally substituted aminoalkyl group with 1-8 C atoms in the alkyl part or piperidinyl group, or R ₂₇ and R ₂₈ together with the N atom form an alkyl group-substituted or unsubstituted pyrrolidine, piperidine or morpholine ring, and R _{29 is} hydrogen or C ₁ -C ₁₈ alkyl optionally substituted with -OH. 4. Compounds according to claim 1 of formula I., wherein M ^q ⊕ Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al ³⁺ , and q is 2 or 3, and

Is hydrogen, C ₁ -C ₄ alkyl or phenyl, or Z _{2 is} also one of groups XIII or XIV, wherein R _{6 has} the meaning given above, and R ₂₂ and R _{23 are} independently hydrogen, methyl or ethyl, and Z _{3 is} hydrogen, or Z ₂ and Z ₃ together mean one of the formulas XV, XVI or XVII, in which R _{6 has} the meaning given above, and R _{24 is} hydrogen or methyl, and ^R _{25 is} C ₁ -C ₈ alkyl, allyl, or one of the groups - ^CH ₂ -COOR ₂₆ or -CH ₂ -CH (R ₈ ) -OR ₆ , in which R ₆ and R _{8 have} the meaning given above, and R _{26 is} C ₁ -C ₈ alkyl, and m is 0.1 or r 2, and AH _{2 is} 0 or an amine of formula XVIII, wherein R ₂₇ and R ₂₈ independently of one another are C ₁ -C ₈ alkyl, C ₁ -C ₆ hydroxyalkyl or a substituted aminoalkyl group of the formula VIIb

is where R ₁ , R ₁₁ and R _{14 have} the meaning given and v is 1 to 8, or R ₂₇ and R ₂₈ together with the N atom form a piperidine group, and _{R29 is} hydrogen, C ₁ -C ₈ alkyl or C ₁ -C ₆ hydroxyalkyl wherein d is 2 to 6, and R _{12 is} a group of the formula VII, in which R ₁ and Z _{1 have} the meaning given above, or Z ₂ also denotes a group of the formula VIII, in which X 'is -O- or -NR ₁₄ , where R _{14 is} hydrogen or methyl, and ^R ₁₃ - ( ^CH ₂ ) _e - or a group

is where e is 0 to 8, and R ₁₅ and R _{16 are} independently hydrogen, C ₁ -C ₄ alkyl, allyl, benzyl, or cyanomethyl, or Z _{2 is} also a group of formula XI, wherein R _{20 is} a group of formula V as defined above, and ^R _{21 is} C ₂ -C ₆ alkylene or phenylene, or Z _{2 is} also a group of the formula XIIa, in which a, b, c, R ₆ and R ₈ have the meaning given above, and f is 0 or 1, and X ₁ -0- or

means what

Hydrogen, C ₁ -C ₈ alkyl, cyclohexyl, C ₃ -C ₈ alkoxyalkyl, C ₇ -C ₈ aralkyl, optionally phenyl monosubstituted with C ₁ -C ₃ alkyl and / or C ₁ -C ₂ alkoxy or if a, b and c 1 and Y _{1 are} -0-, also a group -CH ₂ -CH ₂ -OR ₆ , in which R _{6 has} the meaning given above, and

furthermore means a group VI, wherein R _{1 has} the meaning given above, and R _{11 is} hydrogen or methyl, and Y ₁ - ₀ - or

means what ^R ₁₃ - (CH ₂ ) - or a group

is where e is 0 to 8, and R ₁₅ and R _{16 are} independently hydrogen, C ₁ -C ₄ alkyl, allyl or benzyl, or Z _{2 is} also a group of formula XI, wherein R _{20 is} a group of formula V with the meaning given above, and _{R21 is} C ₂ -C ₆ alkylene, or Z _{2 is} also a group of the formula XIIa, in which a, b, c, R ₆ and R ₈ have the meaning given above, and f is 0 or 1, and X ₁ -0- or

means what

Is hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ alkoxyalkyl, C ₇ -C ₈ aralkyl, optionally phenyl monosubstituted with methyl, methoxy or ethoxy or a group VI, wherein R _{1 has} the meaning given above, and R _{11 is} hydrogen or methyl, and Y _{1 is} -0-, or Z _{2 is} also one of groups XIII or XIV, in which R _{6 has} the meaning given above, and R ₂₂ and R _{23 are} independently hydrogen or methyl, and Z _{3 is} hydrogen, or Z ₂ and Z ₃ together mean one of the formulas XV, XVI or XVII, in which R _{6 has} the meaning given above, and ^R _{24 is} hydrogen, and Z ₂₅ C ₁ -C ₈ alkyl, or one of the groups -CH ₂ COOR ₂₆ 5. Compounds according to claim 1 of formula I, wherein M is ^{q +} Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al ³⁺ , and q is 2 or 3, and r is 1 or 2, the quotient q / r being 1, 1.5, 2 or 3, and L is a group of formula II, wherein R _{1 is} hydrogen, and Z _{1 represents} hydrogen, methyl, acetyl or a group of the formula III, where R _{6 represents} a group of formula V, wherein R _{9 is} hydrogen, and R _{7 is} hydrogen and R _{8 is} hydrogen or methyl, and a is 0, 1 or 2, and b 0 or 1 and c is 0 or, if a and / or b are different from 0, is also 1, and X is -0-, and _Y -

-R ₁₀ means where R _{10 is} hydrogen, and Z _{Z is} hydrogen, C ₂ -C ₇ aliphatic acyloxy, benzoyloxy, an acylamido group optionally substituted with methyl N, or one of the groups

or

where d is 2 to 6, and R _{12 is} a group of the formula VII, in which R ₁ and Z _{1 have} the meaning given above, or Z _{2 is} also a group of formula VIII, wherein X '-O- or -

-R ₁₄ means where R _{14 is} hydrogen or methyl, and