EP0000700A1 - Complexes de métaux avec un anion chélatant portant un groupe phénolique, leur préparation et leur emploi comme stabilisants contre la lumière, en particulier pour des substances polymères - Google Patents

Complexes de métaux avec un anion chélatant portant un groupe phénolique, leur préparation et leur emploi comme stabilisants contre la lumière, en particulier pour des substances polymères Download PDF

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EP0000700A1
EP0000700A1 EP78100325A EP78100325A EP0000700A1 EP 0000700 A1 EP0000700 A1 EP 0000700A1 EP 78100325 A EP78100325 A EP 78100325A EP 78100325 A EP78100325 A EP 78100325A EP 0000700 A1 EP0000700 A1 EP 0000700A1
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group
alkyl
formula
hydrogen
alkenyl
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Michael Dr. Rasberger
Samuel Dr. Evans
Paul Dr. Moser
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00

Definitions

  • the present invention relates to new metal complexes of double or triple charged metal cations with a chelating anion containing phenolate groups, 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. These are mixtures of metal salts and sterically hindered amines.
  • Y is especially one with 1-12 C atoms, preferably ⁇ -unbranched, especially with 1-4 C atoms and very particularly methyl.
  • Y is in particular one with 3-12, especially with 3-6 C atoms, such as allyl, methallyl, n-hex-3-enyl, n-oct-4-enyl and n-undec-10-enyl.
  • Y is in particular one having 3-6 C atoms, such as propargyl, n - but-1-ynyl, but-2-ynyl and n-hex-1-ynyl.
  • the alkyl part can contain 1-3 C atoms and the alkoxy part can consist of 1-18 C atoms, such as in methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n- Butoxyethyl, 3-n-butoxyethyl, 2-octoxyethyl or 2-octadecyloxyethyl.
  • Compounds in which Y is an alkoxy group with 2-5 C atoms should be mentioned in particular.
  • Y is an aralkyl with 7-9 C atoms, e.g. Benzyl or a-phenylethyl.
  • Y as an aliphatic acyl group is in particular one with 1-4 C atoms, for example formyl, acetyl, acryloyl or crotonyl, in particular acetyl.
  • R 6 is C 1 -C 12 alkyl, for example methyl, ethyl, isopropyl, n-butyl, isobutyl, t-butyl, isopentyl, n-octyl, n-decyl or n- Dodecyl; R 6 is preferably C 1 -C 4 alkyl or R 6 is C 3 -C 6 alkenyl, for example allyl, 2-butenyl or 2-hexenyl or C 7 -C 8 aralkyl, for example benzyl or ⁇ -phenylethyl or finally C 5 -C 7 Cycloalkyl, especially cyclohexyl.
  • R 7 is hydrogen, methyl or phenyl, in particular hydrogen.
  • R 8 is an aliphatic C 1 -C 18 acyl radical, for example formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl or acryloyl.
  • R8 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, ⁇ - (3,5-di-t-butyl-4-hydroxyphenyl) propionyl.
  • R 8 is an alicyclic C 6 -C 9 acyl group, it can be cyclohexylcarbonyl or 2,4-dimethylcyclohexylcarbonyl.
  • a preferred meaning of R 8 is also hydrogen.
  • R 9 is C 1 -C 12 alkyl, for example methyl, ethyl, isobutyl, t-butyl, n-hexyl, n-octyl, n-decyl or n-dodecyl.
  • Preferred R 9 are alkyl groups with 1-4 C atoms.
  • R 9 is in particular cyclohexyl or phenyl.
  • R 12 , R 13 and R 14 mean, 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.
  • R 12 and can also mean C 5 -C 12 cycloalkyl, which can be, for example, cyclopentyl, cyclohexyl, 4-methylcyclohexyl or 4-tert-butylcyclohexyl.
  • R 12 can also have the meaning of C 6 -C 18 aryl, which can be, for example, phenyl, tolyl, xylyl, tert-butylphenyl or dodecylphenyl.
  • R 12 as aralkyl can mean -C 7 -C 20 aralkyl and is, for example, benzyl, 4-methylbenzyl. 4-t-butylbenzyl or 4-dodecylbeazyl, especially benzyl.
  • R 12 and R 13 is a ridinyl distrip e, so these are preferably one of the formula (IIa) wherein R 10 is a trivalent radical -CH 2 -CH-CH 2 -.
  • 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, n-octyl and especially n-butyl, in particular Ca 2+ , Mg 2+ , Zn 2+ , Co 2+ , and especially Ni 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
  • r is 1 or 2 and corresponds to the number of phenolate anions in ligand L.
  • a ligand molecule contains several phenolic -OH groups; It depends on the corresponding stability constants and the ratio M / L whether all phenolic OH groups are depratonated and thus contribute to the total charge r - of the ligand L.
  • t indicates the denticity of the ligand L with 2, 3 and 4, ie that t describes the number of donor atoms in the molecule which interact directly with the metal center M q + .
  • 2-, 3- and 4-toothed (dentate) ligands for the task in question, the resulting metal complexes being uncharged.
  • the chelating agent L must meet the condition that it contains at least one of groups IIa or IIb.
  • the symbols R 10 and R 11 have a meaning that the groups IIa and IIb represent, for example, derivatives of pyrrolidine, imidazolidine, 1,4-diazacycloheptanone, piperazine, l-aza-4-thiacyclohexane, dipiperidyl and especially piperidine .
  • R15 and R16 are independently of one another C 1 -C 18 alkyl, it is, for example, methyl, ethyl, isopropyl, n-butyl, t-butyl, amyl, n-hexyl, n-octyl, t-octyl, n -Decyl, n-dodecyl, n-octadecyl or 2-ethyl-hexyl act.
  • Preferred alkyl groups are those with 1-5 C atoms.
  • the alkyl groups can be substituted by a group of the formulas Va, Vb or Vc, preferably Va or Vc; alkyl groups with 1-4 carbon atoms are preferred.
  • Preferred compounds of the formula I are those in which at most one of the radicals R 15 and R 16 is substituted by a group of the formulas Va., Vb or Vc.
  • the radicals -R 15 or R 16 can also be
  • One of the radicals R 15 and R 16 can be a group of the formula VI Buch. For synthetic reasons, this must be in the p-position to the phenolate oxygen.
  • R 15 and R 16 are halogen, it can be chlorine or bromine, in particular chlorine.
  • R 17 as C 1 -C 18 alkyl is, for example, methyl, ethyl, propyl, butyl, n-hexyz, n-octyl, n-decyl, n-dodecyl or n-octadecyl; alkyl groups with 1-12 C atoms are preferred.
  • R 17 is in particular chlorine.
  • R 17 is hydrogen, -OR 24 and in particular a group of the formula Vc.
  • R 20 and R 27 are C 7 -C 14 aralkyl, it can be, for example, benzyl, ⁇ -phenylethyl or 2-phenylpropyl, in particular benzyl.
  • R 20 , R 24 ' R 25 and R 27 are C 1 -C 18 alkyl, for example methyl, ethyl, isopropyl, n butyl, t-butyl, amyl, n-hexyl, n-octyl, t- Octyl, n-decyl, n-dodecyl.
  • alkyl groups with 1-12 C atoms are preferred.
  • Alkyl groups which are substituted by a group of the formula Vc are also preferred, including in particular those having 1-4 C atoms.
  • R 20 , R 24 and R 27 are as, C 2 -C 12 ALkenyl, for example allyl. Amethyally n-hex-3-enyl, n-oct-4-enyl or n-undec-10-enyl. Preference is given to alkenyl groups with 2-6 C atoms, which can optionally be substituted by a group of the formula Vc.
  • R 20 and R 27 can also mean C 5 -C 12 cycloalkyl. It is then, for example, cyclopentyl, cyclohexyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, propylcyclohexyl or dehydroncrhthyl-c-nethyl; especially cyclohexyl.
  • R 20 and R 27 are cyeloalkyl, they are preferably substituted by a group of the formal Vc.
  • R 20 , R 24 and R 27 are C 6 -C 14 aryl, this means, for example, alkylphenyl with 1-8 C atoms, in particular with 1-4 C atoms in the alkyl part, but especially phenyl.
  • the aryl ring is preferably substituted with a group of the formula Vc.
  • R 27 can preferably mean a group of the formula VI.
  • R 21 is as C 1 -C 8 alkyl, for example methyl, ethyl, isopropyl, n-butyl, amyl, n-hexyl or n-octyl. Alkyl groups with 1-4 C atoms are preferred, but in particular R 21 is methyl or hydrogen.
  • R 23 and -R 26 are as C 1 -C 18 alkyl, for example methyl, ethyl, isopropyl, n-butyl, t-butyl, amyl; n-hexyl, n-octyl, t-octyl; n-decyl, n-dodecyl; n-octadecyl.
  • R 23 , R 25 and R 26 are - as C 3 -C 6 alkenyl for example. Allyl, methallyl, but-2-enyl, hex-3-enyl, especially allyl.
  • R 23 and R 25 are C 3 -C 4 alkynyl, it is in particular propargyl.
  • R 23 , R 24 and R 25 are as C 5 -C 7 cycloalkyl, for example cyclopentyl, cyclohexyl or methylcyclohexyl, in particular cyclohexyl.
  • R 23 and R 25 are as C 6 -C 10 aryl, for example phenyl, ⁇ -naphthyl ,. or ⁇ -naphthyl, especially phenyl.
  • R 23 and R 25 are C 7 -C 14 aralkyl, it is, for example, benzyl, a-phenylethyl or 2-phenylethyl, in particular benzyl.
  • R 23 is as C 7 -C 14 alkylphenyl, for example 4-t-butylphenyl or 4-methylphenyl.
  • R 24 as C 7 -C 14 aralkyl is, for example, benzyl, a-phenylethyl or 2-phenylpropyl, in particular benzyl.
  • the aryl radical is preferably substituted with a group of the formula Vc.
  • R 24 and R 26 are aliphatic C 1 -C 18 acyl radicals, for example formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl or acryloyl.
  • R 24 and R 26 are as aromatic C 7 acyl radical benzoyl and as araliphatic C 8 -C 9 acyl radical, cinnamoyl, phenylacetyl or phenylpropionyl.
  • the aromatic part is optionally with chlorine, C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl or t-butyl or with C 1 -C 8 Alkozy. such as methoxy, ethoxy, butoxy or octoxy and / or hydroxy.
  • Substituted aromatic acyl groups are, for example
  • An araliphatic substituted acyl group is, for example, ⁇ - (3,5-Di-t-butyl-4 - . Hydroxyphenyl) propionyl.
  • R 24 and R 26 are alicyclic C 6 -C 9 acyl groups, it can be cyclohexylcarbonyl or 2,4-dimethylcyclohexylcarbonyl.
  • R 25 is also a group -CH 2 -CH (R 5 ) -ßR26
  • R 28 as C 1 -C 12 alkylene can be, for example, methylene, dimethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • R 28 as C 6 -C 10 arylene means, for example, phenylene or naphthylene.
  • X 1 in formula Va has the preferred meaning -NR 25 and X 2 in formula Vc in particular -0-.
  • a simply charged anion B of an aliphatic carboxylic acid is in particular an anion of a carboxylic acid R 33 -COOH.
  • R 33 is an optionally substituted aliphatic carbon is hydrogen, which is especially alkyl with 1-25, especially 1-12 C atoms, cycloalkyl with 5-12, especially 5-6 C atoms, or alkenyl with 2-25, especially 2-12 C atoms and before represents vinyl, if necessary. are substituted by halogen, in particular chlorine, hydroxy, alkyl having 1-6 C atoms or alkoxy having 1-6 C atoms.
  • R 33 examples are methyl, ethyl, n-hexyl, n-undecyl, 1-ethyl-n-pentyl, cyclopentyl, cyclohexyl, vinyl, allyl or crotonyl, or 4-chlorobutyl.
  • Examples of a-aminocarboxylic acids are glycine, ⁇ -alanine, valine and isoleucine, which are mono- or disubstituted on the amino group, in particular dnrch-n-alkyl having 1-8 C atoms, such as di-n-octyl; glycine.
  • An example of ⁇ -aminocarboxylic acids is ⁇ -alanine, which is mono- or disubstituted on the amino group, in particular by n-alkyl having 1-8 C atoms, such as di-n-propyl- ⁇ -alanine.
  • a single-charged anion B of an aromatic carboxylic acid is in particular an anion of a carboxylic acid R 34 -COOH, in which R 34 is an optionally substituted aromatic hydrocarbon radical, which is in particular aryl with 6-10 C atoms or aralkyl with 7-14 C atoms. In particular, it can be phenyl, benzyl or phenylethyl, which can be optionally substituted in the aryl part. Substituents in the aryl part are in particular hydroxy, cyclohexyl,
  • R 39 is hydrogen.
  • R 41 and R 42 are, as C 1 -C 12 alkyl, independently of one another, for example methyl, ethyl, isopropyl, t-butyl, amyl, hexyl, t-octyl or n-dodecyl.
  • a singly charged anion B of a phosphinous acid is in particular an anion of a phosphinous acid of the formula wherein R 43 and R 44 independently of one another are alkyl, or phenyl, benzyl or cyclohexyl which is optionally substituted by chlorine, alkyl and / or alkoxy.
  • R 43 and R 44 are alkyl independently of one another, it is in particular alkyl with 1-18 C atoms, such as methyl, ethyl, n-butyl, n-hexyl, .n-octyl, n-dodetyl or n-octadecyl .
  • R 43 and R 44 are independently phengl, benzyl or cyclohexyl; so these can optionally be mono- or disubstituted with chlorine, C 1 -C 4 alkyl and / or C 1 -C 4 alkoxy. It can be 4-methoxyphenyl, 3-chlorobenzyl, 4-butylphenyl, 4-methyleyclohexyl or 3-chloro-4-methylphenyl.
  • R 29 , R 30 and R 31 as alkyl are in particular alkyl with 1-12 C atoms, especially with 1-6 C atoms, such as methyl, ethyl, n Propyl, n-butyl or n-hexyl.
  • R 29 ' R 30 and R 31 are alkenyl, in particular alkenyl with 2-12 C atoms, especially 2-6 C atoms, such as allyl, methallyl or n-hex-3-enyl.
  • R 29 , R 30 and R 31 are as aralkyl, especially those with 7-12 carbon atoms, such as benzyl or phenylethyl.
  • R 29 ' R 30 and R 31 as aryl are in particular those with 6-10 C atoms, such as phenyl, naphthyl or phenyl, substituted with alkyl with 1-12, in particular 1-4 C atoms, such as methyl, ethyl or butyl; with alkoxy with 1-12, especially 1-4 carbon atoms such as methoxy or butoxy or with halogen such as chlorine.
  • R 29 and R 30 is in particular unsubstituted or one which is a substituent, for example C 1 -C 12 alkyl, in particular C 1 -C 6 alkyl such as methyl; C 1 -C 12 alkoxy, especially C 1 -C 4 alkoxy, such as n-butoxy; or halogen, such as chlorine.
  • R 31 is in particular one with 1-12, especially 1-6 C atoms, which carries halogen, such as chlorine, as a substituent. - If R 31 is alkoxy, it is in particular one with 1-12, especially 1-6, carbon atoms, such as methoxy or ethoxy.
  • Preferred simply charged anions B are especially those of an aliphatic or aromatic carboxylic acid, a phosphonic acid or an enol of the formula IX.
  • s has the meaning 0 to 2, and is preferably 0.
  • the Zn 2+ -1 1 complex of di- ⁇ 2-hydroxy-5- [1,2,2,6,6-pentamethyl-piperidin-4-yl] phenyl ⁇ sulfide (4-amino-1 , 2,2,6,6-pentamethylpiperidine) 3 .
  • Ni 2+ -1 2 complex of di- ⁇ 2-hydroxy-5- [2,2,6,6-tetramethylpiperidin-4-yl] phenyl ⁇ sulfide.
  • R 15 is a C 1 -C 4 alkyl group which is O to the hydroxyl group and is substituted by a group of the formula Va or in particular also a group of the formula -OR 24 which is M to the hydroxyl group, in which R 24 is a C 1 -C 4 alkyl group substituted by a group of the formula Vc. and R 16 and R 17 are hydrogen.
  • Ni 2+ -1 2 complex of 2- (2'-hydroxy-5'-t-butylphenyl) -5- (N-benzyl-2,2,6,6-tetramethyl-piperidine-4-oxy- carbonyl) benz triazole ⁇ (triethanolamine) 2 .
  • the Zn 2+ -1 2 complex of 2- ⁇ 2'-hydroxyef '-sec-butyl)' - 4 '- [2 * - di- (1-acetyl-2,2,6,6-tetramethylpiperidine- 4-oxy-carbonyl) hexyl] phenyl ⁇ -4- (1-acetyl-2,2,6,6-tstremethyl-piperidine-4-oxycarbonyl) benzotriazole ⁇ (4-dimethyl-amiao-2,2, 6,6-tetramethyl-piperidine) 2 .
  • Ni 2+ -1 2 complex of 2- ⁇ 2'-hydroxy-3'-sec-butyl) -4 '- [1,2,2,6,6-pen.tamethyl-piperidine-4-oxycarbonylj -phenyl ⁇ -benz- triazole. (N, N'-Methyl-N, N '- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ethylenediamine.
  • the Al 3+ -1 3 complex of N-phenyl-N- (2-hydroxyphenyl) -N- [2 '- (1-benzyl-2,2,6,6-tetramethyl-piperidine-4-oxy- carbonyl) phenyl] azomethine.
  • Ni 2+ -1 1 complex of hexamethylene-di- ⁇ N-methyl- [2-hydroxy-5- (1 '-, 2', 2 ', 6', 6'-pentamethyl-piperidin-4 ' -yl)] - azomethins (triethanolamine) 2 .
  • the Ca 2+ -1 2 complex of N- (1,2,2,6,6-pentamethyl-piperidin-4-yl) -Nn-butyl-N - ([2'-hydroxy-5'-t octyl] benzyl) amines (dibenzylpropylamine) 2 .
  • Ni 2+ -1 2 complex of hexamethylene-di- ⁇ N- [2-hydroxy-4- (1'-hexyl-2 ', 2', 6 ', 6'-tetramethyl-piperidine-4'- oxy-carbonyl-methyl-oxy)] - benzyl-amine ⁇ (triethanolamine) 2 .
  • the Mg 2+ -1 2 complex of 2- ⁇ 1 ', 2', 2 ', 6', 6'-pentamethylpiperidine-4-oxycarbonyl ⁇ -4- ⁇ 1 ', 2', 2 ', 6' , 6'-pentamethylpiperidine-4-oxycarbonyl-methyl-oxy ⁇ phenol ⁇ (4-dimethylamine-2,2,6,6-tetramethyl-piperidine) 2 .
  • Ni 2+ -1 2 complex of 2-methyl-carbonyl ⁇ -3,5-di- 2 ', 2', 6 ', 6'-tetramethyl-piperidine-4-oxycarbonyl-methyloxy ⁇ - phenol Triethanolamine) 2 .
  • the compounds of the formula I in which s and m are 0 are most easily obtained by mixing about one mole of the free ligand [L] H r with about r / * moles of an alkali metal or alkaline earth metal hydroxide, alcoholate, hydride or -Amids or also r / 2q * moles of an alkali or alkaline earth carbonate in an inert, organic solvent.
  • the reaction can take place at room temperature or to accelerate the reaction at elevated temperatures up to the reflux temperature. The easiest way to work is at room temperature.
  • Particularly suitable alkali metals are lithium, sodium, potassium or rubidium, especially sodium or potassium. Calcium is particularly suitable as an alkaline earth metal.
  • q * defines the charge of the alkali or alkaline earth metal cation M * used.
  • Alcohols such as methanol or ethanol, ethers such as dioxane, tetrahydrofuran or diethyl ether are suitable as inert organic solvents; aromatic hydrocarbons such as benzene, taluol, xylene; aliphatic hydrocarbons such as hexane or ligroin; or amides such as dimethylformamide or hexamethylphosphoric triamide.
  • the alkali or alkaline earth salts obtained in this way can then be easily implemented with a metal salt ML * q .
  • All q / r moles of the compound [L] M * r / q * per mole of ML * are used in an inert organic solvent.
  • the solvents described above are suitable as solvents.
  • the temperature can in turn be selected from room temperature to the reflux temperature.
  • Particularly suitable as anion L * are halogenic, especially chloride, or carboxylate anions, such as acetate or capronate.
  • the compound of the formula I is to contain an amine A
  • the simplest solution is to use a solution of the compound [M q + ] [L r- ] (qs) / r ⁇ [B - ] s in one of the described processes aprotic inert solvent heated in the presence of at least m moles of compound A.
  • the temperature can be up to the reflux temperature, but should in any case be at least 30 ° C.
  • Advantageous results are achieved by refluxing, using a water separator.
  • the amines A are known and can be prepared by known methods. Some such compounds are described, for example, in U.S. Pat. 3,901,031 or if A contains piperidyl residues also described in DT-OS 2,349,962.
  • a chelating ligand according to The present invention must meet that it contains at least one group of formula IIa or IIb. How to obtain compounds which contain groups IIa or IIb has been described in the literature. For example, derivatives of pyrrolidine in DT-OS 2,459,331; of the Imidazoli.
  • the 4-oxopiperidines of the formula XVII, in which Y is hydrogen, can be prepared by various processes.
  • the compounds of the formula XVIII are reacted in a second process step with ammonia and a ketone CH 3 -CO-CH 2 -R 21 , as described, for example, in 'Monthly. Chemie 88, 464 (1957).
  • the compounds of formula XVII, in which Y is hydrogen, can be obtained from the pyrimidine thus obtained by hydrolysis.
  • the group -CH 2 -CH (R 7 ) -OR 8 can by reacting the NH-piperidines with an epoxide of the formula and subsequent acylation with an acyl chloride of the formula R 8 Cl are introduced. Analogously, a hydroxyalkyl radical can be introduced.
  • R 22 is based on the 4-hydroxy.
  • 4-aminopiperidines by customary methods, for example by reaction with a chloride of the formula R 26 Cl, or hydrogenolytic condensation with H 2 NR 26 -
  • R 15 or R 16 is an alkoxy group which is substituted by a radical of the formula Vc, their on occurs leadership, for example, by the reaction of a phenol, such as a catechol, resorcinol, hydroquinone, pyrogallol, or phloroglucin with a haloalkyl derivative of the group of the formula Vc in an inert solvent in the presence of a base.
  • R 15 or R 16 is a group of the formula VI
  • a phenol is reacted with a 4-oxo derivative of a group of the formula VI in the presence of an acid and subsequent reduction, as described, for example, in US Pat. 3,847,930.
  • L is a group of the formula IVa
  • its preparation can be carried out analogously to the description in US Pat. 2,971,941 take place, about 2 moles of a phenol being reacted with 1 mole of SCl 2 and the introduction of the radicals R 15 and R 16 as described above takes place before or after the SCl 2 stage.
  • R 15 is a group of the formula VI, this is introduced before the SCl 2 stage.
  • the chelating agents H 2 L corresponding to formula IVa thus prepared are new and therefore form an object of the present invention.
  • Compounds which contain a group of the formula IVa are distinguished by the fact that r can have a value of 1 or 2. This depends on the ratio of the onset concentration of the free ligand and the metal salt in the chelation step described above.
  • L is a group of the formula IVb
  • its preparation can be carried out analogously to the compounds from GB Pat. 878,362 or GB Pat. 1,332,560.
  • R 15 or R 16 contain a group IIa or IIb, or Va, Vb or VI, these are introduced as described above.
  • R 17 is a group of the formula Vc in which R 23 is a radical of the formula VI, the known compounds are used in which R 23 means alkyl, and esterifies it with an alcohol derived from group Va in a known manner.
  • R 17 is a group of the formula -OR 24 , the simplest way to react the analogue compound in which R 17 is hydroxy with a compound CLR 24 .
  • Some of the chelating agents of formula IVb are known from JA-OS 51-88484.
  • L is a group of the formula IVc, if R 15 or R 16 contain a group IIa or IIb or Va, Vb or VI, these are introduced as described above.
  • R 18 and R 19 together 0, salicylic acid or its alkyl ester, salicylamide or an a-hydroxyphenyl ketone are generally used as starting materials.
  • the introduction of a group of the formula Va as R 20 is therefore carried out by a simple transesterification reaction starting from a salicylic acid ester with an alcohol or amine, which is derived from the formula Va.
  • compounds can be prepared by transesterification in which R 20 denotes an alkyl, alkenyl, cycloalkyl or aryl group substituted by a group of the formula Vc.
  • Known compounds can be obtained from the keto compounds thus obtained
  • the keto compounds are reacted with a primary amine in a common condensation reaction.
  • This can be an amine which is derived from a group of the formula Va, in which X 1 is -NH, or it can also be an alkyl, alkenyl, cycloalkyl or arylamine which is substituted by a group of the formula Vc .
  • the compounds in which R 27 is a group of the formula VIIIb are obtained by replacing the primary amine with a diamine and reacting with 2 moles of the keto compound.
  • the described azomethine compounds of the formula IVc can be reduced to the compounds of the formula IVc by known reduction methods, for example by means of hydrogen to Pd / C, in which X 1 denotes -NH.
  • Another variant is to use a secondary amine HN (R 25 ) R 27 in a Mannich reaction in the presence of an aldehyde, preferably formaldehyde. If the chelating agent contains a group of the formula VIIIa as R 27 , the preparation is carried out by reducing the corresponding di-azomethine compound.
  • the compounds of the formula IVc obtained in the manner described, in which R 18 denotes -N (R 25 ) R 27 are new and therefore also constitute an object of the invention.
  • the molecular weight is approximately 400-10000, preferably 400-2000.
  • the compounds of the formula I can be used as stabilizers for plastics against their damage by the action of oxygen, heat and light.
  • plastics are the polymers listed in DT-OS 2,456,864 on pages 12-14.
  • polyolefins styrene polymers and polyurethanes
  • examples include high and low density polyethylene, polypropylene, ethylene-propylene copolymers, polystyrene, styrene-butadiene-acrylonitrile copolymers, mixtures of polyolefins or of styrene polymers, polyurethanes based on polyether or polyester in the form of films, fibers, lacquers, 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.
  • concentration of 0.01 to 5% by weight, calculated on the material to be stabilized.
  • 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.
  • 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.
  • Stabilizer 21 has the following analysis data:
  • 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 during exposure is a measure of the photooxidative degradation of the polymer (sLBlaban et al., J. Polymer Sci. Part C, 22,
  • the measure of the protective effect is the time until a carbonyl extinction of 0.100 is reached.
  • the exposure time up to 50% loss of tensile strength is the measure of the protective effect.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Hydrogenated Pyridines (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
EP78100325A 1977-07-15 1978-07-07 Complexes de métaux avec un anion chélatant portant un groupe phénolique, leur préparation et leur emploi comme stabilisants contre la lumière, en particulier pour des substances polymères Withdrawn EP0000700A1 (fr)

Applications Claiming Priority (2)

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CH879477 1977-07-15
CH8794/77 1977-07-15

Publications (1)

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EP0000700A1 true EP0000700A1 (fr) 1979-02-21

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EP78100325A Withdrawn EP0000700A1 (fr) 1977-07-15 1978-07-07 Complexes de métaux avec un anion chélatant portant un groupe phénolique, leur préparation et leur emploi comme stabilisants contre la lumière, en particulier pour des substances polymères

Country Status (4)

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US (1) US4263202A (fr)
EP (1) EP0000700A1 (fr)
JP (1) JPS5419984A (fr)
IT (1) IT7825734A0 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3669154D1 (de) * 1985-12-06 1990-04-05 Ciba Geigy Ag Verfahren zur herstellung von 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy-piperidin.

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2042652A1 (de) * 1969-08-27 1971-03-04 American Cyanamid Co , Wayne, N J (V St A) Thiobisphenol Nickel Alkanolamm Komplexe
GB1365319A (en) * 1970-09-19 1974-08-29 Ciba Geigy Ag Teromethyl piperidine compounds and compositions containnig them
DE2436616A1 (de) * 1973-08-07 1975-02-27 Ciba Geigy Ag Nickel-stabilisatoren fuer synthetische polymere
US3879396A (en) * 1973-12-28 1975-04-22 Ciba Geigy Corp Bicyclic hindered amino acids and metal salts thereof
US4001181A (en) * 1973-12-28 1977-01-04 Ciba-Geigy Corporation Hindered piperidine carboxamide acids, metal salts thereof, and stabilized compositions
DE2625967A1 (de) * 1975-06-19 1977-04-07 Ciba Geigy Ag Neue lichtschutzmittel
US4026866A (en) * 1972-06-21 1977-05-31 Ciba-Geigy Corporation Nickel stabilizers for synthetic polymers

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3464953A (en) * 1967-02-14 1969-09-02 Eastman Kodak Co Stabilized polyolefins
GB1395159A (en) * 1971-11-30 1975-05-21 Ciba Geigy Ag Tetra-hydropyridine derivatives
US3992390A (en) * 1971-11-30 1976-11-16 Brian Holt Esters of piperidinols
CH562301A5 (fr) * 1971-12-13 1975-05-30 Ciba Geigy Ag
US3745163A (en) * 1972-03-13 1973-07-10 Ciba Geigy Corp 2,2,6,6-tetramethyl piperidinyl-4-(dialkyl-hydroxy-benzoyl or phenyl alkanoyl)hydrazones
CH567557A5 (fr) * 1972-08-09 1975-10-15 Ciba Geigy Ag
US4052361A (en) * 1974-12-30 1977-10-04 American Cyanamid Company N-(2,2-dimethyl-6,6-di(lower alkyl)-4-piperidinyl)-amides of hindered 3,5-dialkyl-4-hydroxybenzoic acids and use as light stabilizers in polyolefins

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2042652A1 (de) * 1969-08-27 1971-03-04 American Cyanamid Co , Wayne, N J (V St A) Thiobisphenol Nickel Alkanolamm Komplexe
GB1365319A (en) * 1970-09-19 1974-08-29 Ciba Geigy Ag Teromethyl piperidine compounds and compositions containnig them
US4026866A (en) * 1972-06-21 1977-05-31 Ciba-Geigy Corporation Nickel stabilizers for synthetic polymers
DE2436616A1 (de) * 1973-08-07 1975-02-27 Ciba Geigy Ag Nickel-stabilisatoren fuer synthetische polymere
US3879396A (en) * 1973-12-28 1975-04-22 Ciba Geigy Corp Bicyclic hindered amino acids and metal salts thereof
US4001181A (en) * 1973-12-28 1977-01-04 Ciba-Geigy Corporation Hindered piperidine carboxamide acids, metal salts thereof, and stabilized compositions
DE2625967A1 (de) * 1975-06-19 1977-04-07 Ciba Geigy Ag Neue lichtschutzmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, 71, 49713q (1969) & IZV. NAUK AKAD. SSSR, Ser. Klim., 1969(3) 698-700 *

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IT7825734A0 (it) 1978-07-14
US4263202A (en) 1981-04-21

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