DE10011317A1 - Use of amino-substituted hydroxybenzophenones as photoprotective agents and stabilizers for nonliving organic materials, especially plastics, polymer dispersions, lacquers and photographic emulsions - Google Patents

Abstract

Amino-substituted hydroxybenzophenones (I) are used as photoprotective agents and stabilizers for nonliving organic materials. Amino-substituted hydroxybenzophenones of formula (I) are used as photoprotective agents and stabilizers for nonliving organic materials: R<1>, R<2> = H, 1-20C alkyl, 2-20C alkenyl, 3-10C cycloalkyl or 3-10C cycloalkenyl or together form a 5- or 6-membered ring; R<3>, R<4> = 1-20C alkyl, 2-20C alkenyl, 3-10C cycloalkyl, 3-10C cycloalkenyl, 1-20C alkoxy, 1-20C alkoxycarbonyl, mono- or di(1-20C alkyl)amino, optionally substituted aryl or heteroaryl; X = H, COOR<5> or CONR<6>R<7>; R<5>-R<7> = H, 1-20C alkyl, 2-20C alkenyl, 3-10C cycloalkyl, 3-10C cycloalkenyl, (YO)qZ or optionally substituted aryl; Y = (CH2)2, (CH2)3, (CH2)4 or CH(Me)CH2; Z = Et, n-Pr, n-Bu or i-Pr; m = 0-2; n = 0-4; q = 1-20. An Independent claim is also included for nonliving organic materials containing (I) as photoprotective agents and stabilizers.

Description

The present invention relates to the use of aminosub substituted hydroxybenzophenones as light stabilizers and stabilizers lisators for non-living organic material, in particular Plastics, plastic dispersions, lacquers and photographic Emulsions or layers, as well as non-living organic mate rial, which amino-substituted hydroxybenzophenones as light contains protective agents and stabilizers, in particular it acts are plastics, plastic dispersions, paints and photographic emulsions or layers.

Substituted hydroxybenzophenones and their use as UV-Ab sorbers are known from the literature. So are in the document EP 0 727 320 A1 such Hydroxybenzophenone as UV-absorbing Zu sentences described in laser-writable components. According to the formula shown therein may a. also alkylamino, arylamino and Amino as possible substituents on the aromatic rings of the Hydroxybenzophenones in question, among the examples listed However, compounds only disclose a hydroxybenzophenone derivative a diethylamino substituent, which is also attached to the benzene ring is bound, which does not carry the hydroxy group.

In Japanese laid-open publications Shyo63-254151 and Shyo 61-282335, U.S. Patents 3,120,564, 3,215,759 and 3,981,822 and published patent application DT 23 35 444 are even if hydroxybenzophenones as UV absorbers for polymers and copo polymeric or known in organic compositions. As possible che substituents of the aromatic rings are u. a. Amino, alky lamino or substituted amino group listed. None of these Writings, however, lists hydroxybenzophenone derivatives, which ei (Substituted) amino substituents on the, the hydroxy Own a group bearing a benzene ring.

Japanese published patent application Hei 2-248951 describes photo resist compositions which contain 2- (C ₁ -C ₈ alkyl) -, 2-acetyloxy- or 2-hydroxy-4- (substituted) aminobenzophe none as UV absorber. The substituent of the second benzene ring, in a position not specified further, is the carboxyl or C ₁ -C ₄ -alkyloxycarbonyl group. In this document, the compounds of the formulas I and Ia according to the present application are not mentioned, nor is their use in the sense of the present application described.

In the older German application 199 17 906.9, the Verwen Amino substituted hydroxybenzophenones similar to Verbin of formula I of the present application as photostable UV filters for cosmetic or pharmaceutical preparations wrote. These UV filters are primarily used to protect life the tissue, especially the human skin. On the suitability water compounds as light stabilizers and stabilizers for non-living organic material will not be accepted gene.

The object of the present invention was to provide light stabilizers or To provide stabilizers that are effective and possible Long-term protection for non-living organic mate rial, especially for plastics, plastic dispersions, paints or photographic emulsions or layers.

Accordingly, the use of amino-substituted hydroxybenzophenones of the general formula I

in which the variables each have the following meaning independently of one another:
R ¹ , R ^{2 are} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, where R ¹ and R ² together with the nitrogen atom to which they are attached can form a five- or six-membered ring,
R ³ , R ⁴ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylamino, di (C ₁ -C ₂₀ alkyl) amino, optionally substituted aryl or heteroaryl,
X hydrogen, COOR ⁵ , CONR ⁶ R ⁷ ,
R ⁵ , R ⁶ , R ^{7 are} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, - (YO) _q -Z , optionally substituted aryl,
Y - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH (CH ₃ ) -CH ₂ -,
Z -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ ,
m values of 0, 1, 2 or 3,
n values of 0, 1, 2, 3 or 4 and
q integer values from 1 to 20,
as light stabilizers and stabilizers for non-living organic material, in particular for plastics, plastics dispersions, lacquers or photographic emulsions or layers, ge found.

As C ₁ -C ₂₀ alkyl radicals for R ¹ to R ⁷ are branched or unbranched alkyl chains, such as. B. methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2nd , 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2 -Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2- Trimethyl propyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl called n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl.

As C ₂ -C ₂₀ alkenyl radicals for R ¹ to R ⁷ are branched or unbranched alkenyl chains, such as. B. vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1- Hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1-nonenyl, 2-none nyl, 1-decenyl, 2-decenyl, 1-undecenyl, 2-undecenyl, 1-dodecenyl , 2-dodecenyl, 1-tridecenyl, 2-tridecenyl, 1-tetradecenyl, 2-tetra decenyl, 1-pentadecenyl, 2-pentadecenyl, 1-hexadecenyl, 2-hexadecenyl, 1-heptadecenyl, 2-heptadecenyl, 1-octadecenyl , 2-Octadece nyl, 1-nonadecenyl, 2-nonadecenyl, 1-eicosenyl or 2-eicosenyl called.

As C ₃ -C ₁₀ cycloalkyl radicals for R ¹ to R ⁷ are branched or unbranched cycloalkyl chains, such as. B. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-1-butylcyclopropyl, 1,2-dimethylcyclypropyl, 1-methyl- Called 2-ethylcyclopropyl, cyclooctyl, cyclononyl or cyclodecyl.

As C ₃ -C ₁₀ cycloalkenyl radicals for R ¹ to R ⁷ are branched or unbranched cycloalkenyl chains with one or more double bonds, such as. B. cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohe xadienyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, 1,5-cy clooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecenyl.

As C ₁ -C ₂₀ alkoxy radicals for R ³ and R ⁴ are those which z. B. derived from the above-mentioned C ₁ -C ₂₀ alkyl radicals.

As C ₁ -C ₂₀ alkoxycarbonyl radicals for R ³ and R ⁴ come into consideration those which z. B. derive from the aforementioned C ₁ -C ₂₀ alkoxy most.

As C ₁ -C ₂₀ alkylamino and di (C ₁ -C ₂₀ alkyl) amino radicals for R ³ and R ⁴ are those which z. B. derived from the above-mentioned C ₁ -C ₂₀ alkyl radicals. The alkyl residues of the di (C ₁ -C ₂₀ alkyl) amino residues can be different. However, they are preferably the same.

Aryl for R ³ to R ⁷ are to be understood as aromatic rings or ring systems with 6 to 18 carbon atoms in the ring system, for example phenyl or naphthyl, which may optionally contain one or more radicals such as halogen, e.g. B. fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -dialkylamino, Hy droxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy can, wherein the C ₁ -C ₄ alkyl radicals in the optionally present substituents are already mentioned among the C ₁ -C ₂₀ alkyl radicals listed above as examples. Substituted phenyl, methoxyphenyl and naphthyl are preferred.

Heteroaryl for R ³ and R ⁴ are to be understood as residues B. of pyrrole, furan, thiophene, pyrazole, isoxazole, isothiazole, imidazole, 1H-1,2,3-triazole, 1H-1,2,4-triazole, pyridine, pyrazine, pyridazine, 1H-azepine, 2H- Azepine, oxazole, thiazole, 1,2,3-, 1,2,4- or 1,3,4-oxadiazole, 1,2,3-, 1,2,4- or 1,3,4-thiadiazole as well optionally the benzo or dibenzoa fused rings such. B. quinoline, isoquinoline, indole, benzo [b] furan (coumarone), benzo [b] thiophene (thionaphthene), carbazole, dibenzofuran, dibenzothiophene, 1H-indazole, indoxazole, benzo [d] isothiazole, anthranil, benzimidazole, benzoxazole Derive benzo thiazole, cinnoline, phthalazine, quinazoline, quinoxaline or phena zin and optionally with one or more radicals such as halogen, for. B. fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy may be substituted , where the C ₁ -C ₄ -alkyl radicals in the substituents which may be present are already mentioned among the C ₁ -C ₂₀ -alkyl radicals listed above as examples. The heteroaryl residues can be linked to the benzene rings via a carbon or nitrogen atom. In the latter case, the remainder is bound via a nitrogen atom which carries a hydrogen atom in the underlying heteroaromatic.

A pyrrolidine or piperidine ring can be used as a five- or six-membered ring, which the substituents R ¹ and R ^{2 can form} together with the nitrogen atom to which they are attached. The R ¹ R ² N- group accordingly represents a pyrrolidinyl or piperidinyl radical.

The amino group can be in ortho, meta or para posi tion, relative to the carbonyl group. The is preferred para position.

Preferred uses are compounds of the formula I in which Chen n takes the values 0, 1 or 2 and m takes the values 0 or 1.

Compounds of the formula I, in which n and m are each 0.

Particular preference is given to the use of compounds of the formula Ia according to the invention,

in which the variables each have the following meaning independently of one another:
R ¹ , R ^{2 are} hydrogen, C ₁ -C ₁₂ alkyl, where R ¹ and R ² together with the nitrogen atom to which they are attached can form a five- or six-membered ring, and
X is hydrogen or COOR ⁵ and
R ^{5 is} hydrogen, C ₁ -C ₁₂ alkyl or C ₃ -C ₆ cycloalkyl.
C ₁ -C ₁₂ alkyl radicals for R ¹ , R ² and R ⁵ and C ₃ -C ₆ cycloalkyl radicals for R ⁵ have already been mentioned above under the exemplary performances of possible C ₁ -C ₂₀ alkyl radicals and C ₃ -C ₁₀ alkyl radicals for R ¹ to R ⁷ called.

As C ₃ -C ₆ cycloalkyl radicals for R ⁵ in particular cyclopropyl, cyclopentyl and cyclohexyl may be mentioned.

In particular, compounds of the formula Ia come into question in which R ¹ and R ^{2 are the} same.

Preferred substituents for R ¹ and R ² are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2nd -Methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, hexyl and 2-ethylhexyl or for the grouping R ¹ R ² N-pyrrolidinyl or piperidinyl.

Preferred substituents R ⁵ are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3- Methylbutyl, 2,2-dimethylpropyl, hexyl and 2-ethylhexyl.

Compounds of the formula Ia in which R ¹ and R ^{2 are the} same, X denotes hydrogen or COOR ⁵ and R ¹ , R ² and R ^{5 represent} the radicals mentioned above by way of example are preferred.

The compounds of the formulas I to be used according to the invention and Ia can by direct acylation of the corresponding amino substituted phenols.

For example, the synthesis of 2-hydroxy-4-diethyla mino-2'-methoxycarbonylbenzophenone (1) or 2-hydroxy-4-pyrroli din-1-yl-2'-methoxycarbonylbenzophenone (2) by acylation of 3-diethylaminophenol or 3-pyrrolidin-1-yl-phenol with phthalic acid reanhydride and subsequent esterification.

Furthermore, 2-hydroxy-4-diethylaminobenzophenone (3) can be produced, for example, by reacting meta-diethylaminophenol with benzoyl chloride and then shifting Fries with AlCl ₃ .

Details on the Friedel-Crafts reaction and Fries' Shift can be found in the Organikum, VEB Deutscher Verlag der Sciences, Berlin, 1986, pp. 323-327 and in Houben-Weyl, Vol. 7 / 2a, 1973, pp. 379-389.

The invention by the compounds of formulas I and Ia Stabilized non-living organic material can be given if still contain other additives, e.g. B. antioxidants, Light stabilizers, metal deactivators, antistatic Agents, flame retardants, pigments and fillers.

Antioxidants and light stabilizers, in addition to the compounds gen of formulas I and Ia can be added, for. B. Compounds based on sterically hindered phenols or Costabilizers containing sulfur or phosphorus.

Examples of such phenolic antioxidants are wise 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-β- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris- (2-methyl- 4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (3,5-di- tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- [β- (3,5-di- tert-butyl-4-hydroxybenzyl) propionylethyl] isocyanurate, 1,3,5- Tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate and Pentaerythritol tetrakis [β-3,5-di-tert-butyl-4-hydroxyphenyl) - propionate] mentioned.  

As phosphorus-containing antioxidants there are, for example, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, distearylpentaerythritol phosphite, tris- (2-tert-butyl-4-methylphenyl) phosphite, bis- (2,4- di-tert-butylphenyl) pentaerythritol diphosphite and tetrakis (2,4- di-tert-butylphenyl) -4,4'-biphenylene diphosphite into consideration.

Examples of sulfur-containing antioxidants are wise dilauryl thiodipropionate, dimyristyl thiodipropionate, Distearylthiodipropionate, pentaerythritol tetrakis-β-laurylthio propionate) and pentaerythritol tetrakis - (- β-hexylthiopropionate) called. Furthermore, thiobisphenols such as 3,3'-di-tert-butyl- 4,4'-dihydroxy-2,2'-dimethyl-diphenyl sulfide can be added.

Other antioxidants and light stabilizers that work together with the compounds of the formulas I and Ia can be used, are z. B. 2- (2'-Hydroxyphenyl) benzotriazoles, aryl esters of hydro xybenzoic acids, α-cyanocinnamic acid derivatives, benzimidazole carboxylic acid reanilides, nickel compounds or oxalic acid dianilides.

A particularly good stabilization is obtained when ver bonds of the formulas I or Ia, if appropriate in addition to others mentioned additives, at least one further light stabilizer from the compound class of sterically hindered amines usual concentration is added.

As sterically hindered amines come z. B. into consideration: bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, the condensation product of N, N '- (2,2,6,6-tetrame thylpiperidin-4-yl) -hexamethylene diamine with 4- tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, tetrakis (2,2,6,6- tetramethylpiperidin-4-yl) -1,2,3,4-butane-tetracarboxylic acid, 1,1 '- (1,2-ethanediyl) -bis- (3,3,5,5-tetramethylpiperazinone), polymer-analogous reaction products 4-amino-2,2,6,6-tetramethylpiperidine and maleic acid / C ₂₀ -C ₂₄ -α-olefin copolymers, e.g. B. Uvinul®5050 H (BASF Aktiengesellschaft, Ludwigshafen), and corresponding polymer-analogous reaction products with 4-amino-1,2,2,6, 6-pentamethylpiperidine (e.g. "methylated Uvinul®5050 H"), condensation products from tetramethylolacetylene diurea and 4-amino-2,2,6,6-tetramethyl piperidine, e.g. B. Uvinul®4049 H (BASF Aktiengesellschaft, Ludwigshafen), and corresponding condensation products with 4-amino-1,2,2,6,6-pentamethylpiperidine (eg "methylated Uvinul®4049 H") and N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-bisformyl-1,6-diaminohexane, e.g. B. as Uvinul®4050 H (BASF Aktiengesellschaft, Ludwigshafen).

The compounds of the formulas I or Ia are preferably used, optionally with the addition of one or more of the aforementioned ten additives and / or one or more further light stabilizers gates from the compound class of sterically hindered amines, as light stabilizers and stabilizers for plastics, art material dispersions, lacquers or photographic emulsions or Layers.

Examples of plastics which can be stabilized according to the invention by the compounds of the formulas I or Ia are:
Polymers of mono- and diolefins, such as. B. low or high density polyethylene, polypropylene, linear polybutene-1, polyiso pren, polybutadiene and copolymers of mono- or diolefins or mixtures of the polymers mentioned,
Copolymers of mono- or diolefins with other vinyl monomers, such as. B. ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers,
Polystyrene and copolymers of styrene or α-methylstyrene with dienes and / or acrylic derivatives, such as. B. styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methacrylate, acrylonitrile-butadiene-styrene (ABS) or methyl methacrylate-butadiene-styrene (MBS),
Halogen-containing polymers, such as. B. polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride and their copolymers,
Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates, polymethacrylates, polyacrylamides and polyacrylonitriles,
Polymers derived from unsaturated alcohols and amines or from their acrylic derivatives or acetals, e.g. B. polyvinyl alcohol and polyvinyl acetate and
Polyurethanes, polyamides, polyureas, polyphenylene ethers, polyesters, polycarbonates, polyoxymethylenes, polysulfones, polyether sulfones and polyether ketones.

The compounds of the formulas I or Ia are preferably given if necessary with the addition of one or more of the aforementioned ad ditive and / or one or more other light stabilizers from the compound class of sterically hindered amines, for Stabilizing polyolefins, especially polyethylene, from Polycarbonates, polyamides, polyesters, polystyrene, used by ABS and polyurethanes. In particular, too Films made of the plastics mentioned are stabilized.

You can also give with the compounds of the formulas I or Ia if necessary with the addition of one or more of the aforementioned ad ditive and / or one or more other light stabilizers from the compound class of sterically hindered amines, invented according to plastic dispersions and their filmed plastic products are stabilized. The Ver Bonds of formulas I or Ia preferably after production the dispersion, optionally using conventional dis Pouring aids, added.

For such plastic dispersions, among the polymers or copolymers already mentioned, there are those which can usually be present in the form of a dispersion. In particular, these are dispersions based on:
Copolymers of mono- or diolefins with other vinyl monomers, such as. B. ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers,
Polystyrene and copolymers of styrene or α-methylstyrene with dienes and / or acrylic derivatives, such as. B. styrene-butadienes, styrene-acrylonitriles (SAN), styrene-ethyl methacrylates, styrene-butadiene-ethyl acrylates, styrene-acrylonitrile-methacrylates, acrylonitrile-butadiene-styrenes (ABS) or methyl methacrylate-butadiene-styrenes (MBS) or
Polymers derived from α, β-unsaturated acids and their derivatives, such as. B. polyacrylates, polymethacrylates, poly acrylamides and polyacrylonitriles.

Furthermore, with the compounds of the formulas I and Ia if necessary with the addition of one or more of the aforementioned Additives and / or one or more other light stabilizers from the compound class of sterically hindered amines, invented paints are stabilized according to the invention, especially such paints or Paintwork, which is to a large extent affected by the environment rivers that are exposed to sunlight and heat. these are  e.g. B. paints for exterior painting, industrial or vehicle paint stanchions. Furthermore, these are paints for stove enamels, especially al lem in the automotive sector.

Furthermore, with the compounds of the formulas I and Ia photographic emulsions or photographic Layers are stabilized. The connections serve here of formulas I and Ia primarily as UV stabilizers and / or UV Filters, which the negative influence of UV radiation on the Be durability and the exposure behavior of such emulsions or Reduce layers. If necessary, you can also here, in addition to the compo usual for photographic emulsions or layers nents and additives, including one or more of the aforementioned Additives and / or one or more other light stabilizers add from the compound class of sterically hindered amines.

Another object of the present invention is not le organic material, especially plastics, art material dispersions, lacquers or photographic emulsions or Layers containing compounds of the formulas I and Ia.

Usually the non-living organic material contains ins special plastics, plastic dispersions, lacquers or photo graphic emulsions or layers, the compounds of For meln I and Ia in a proportion of 0.001 to 10 wt .-%, preferred in a proportion of 0.01 to 5 wt .-%, based on the total amount of organic material, stabilizer and if necessary other additives.

Of course, several of the connections of For Meln I and Ia are added, the previously specified Shares then on the total of the shares of the added connection relate to formulas I and Ia.

example 1 Preparation of 2-hydroxy-4-diethylamino-2'-methoxycarbonylbenzo phenon

A solution of 3.11 g (18.8 mmol) of 3-diethylaminophenol and 2.88 g (19.4 mmol) phthalic anhydride in 60 ml of absolute toluene Heated under reflux for 21 h. After removing the solvent in the The residue was dissolved in 100 ml of chloroform in vacuo. The orga phase was six times with 20 ml of dilute hydrochloric acid and washed once with 20 ml water, then six times with 20 ml each saturated sodium bicarbonate solution extracted. The club The aqueous extracts were diluted with sulfuric acid Acidified pH <2 and extracted three times with 50 ml of diethyl ether. The combined ether extracts were three times with 50 ml of water washed and three times with 50 ml of saturated sodium hydrogen extracted carbonate solution. The combined aqueous extracts were acidified to pH <2 and three times with 50 ml of diethyl ether extracted. The organic phases were combined with 50 ml Washed water, dried over magnesium sulfate, filtered and the solvent removed in vacuo.

The crude product was dissolved in 40 ml of absolute methanol and 1 ml of concentrated sulfuric acid and heated under reflux for 19 h. The solvent was removed in vacuo and the residue was taken up in ethyl acetate. Washing with saturated sodium bicarbonate solution and water, drying over sodium sulfate, filtering and removing the solvent gave an oil which was purified by flash chromatography (mobile phase: pentane / acetic ester 80:20). 0.77 g (2.4 mmol) of 2-hydroxy-4-diethylamino-2'-methoxycarbonylbenzophenone were obtained, the structure of which was confirmed by NMR spectroscopy. λ _max : 354 nm; E ¹ ₁ : 1173.

Example 2

Preparation of 2-hydroxy-4-diethylaminobenzophenone

a)

A solution of 2.99 g (18.1 mmol) 3-diethylaminophenol, 2.7 ml (23.6 mmol) benzoyl chloride and 2 ml pyridine in 100 ml absolute Toluene was refluxed for 3 hours. After removing the Lö the crude product by means of flash chromatography  (Eluent: pentane / ethyl acetate 90: 10) cleaned. Man received 0.8 g of 3-diethylaminophenyl benzoate.

b)

0.78 g (2.9 mmol) of 3-diethylaminophenyl benzoate and 1.16 g (8.7 mmol) of aluminum trichloride were mixed and heated at 175 ° C. for 4 h. After cooling, the reaction mixture was hydrolyzed with ice water and 2 ml of concentrated hydrochloric acid. The mixture was stirred at room temperature for 1 h before the reaction mixture was mixed with 50 ml of dichloromethane. The organic phase was separated and the aqueous phase was extracted twice with 10 ml of dichloromethane. The combined organic phases were dried over sodium sulfate, filtered and the solvent removed in vacuo. The crude product was purified by flash chromatography (eluent: pentane / methyl tert-butyl ether 90:10). 0.22 g of 2-hydroxy-4-diethylaminobenzophenone was obtained. M.p .: 46-48 ° C; λ _max : 359 nm; E ¹ ₁ : 1280.

Example 3

Preparation of 2-hydroxy-4-pyrrolidin-1-yl-2'-carboxybenzophenone

3.48 g (21.3 mmol) of 3-pyrrolidin-1-yl-phenol were dissolved in 60 ml of absolute toluene. After adding 3.47 g (23.4 mmol) of phthalic anhydride, the reaction mixture was heated under reflux for 22 h. After cooling, the solvent was removed in vacuo and the residue was taken up in 100 ml of chloroform. The organic phase was washed six times with 20 ml of dilute hydrochloric acid and then with so much water that the aqueous phase contained almost no rhodanine dye. The organic phase was extracted six times with 20 ml of saturated sodium bicarbonate solution. The combined aqueous extracts were acidified with dilute sulfuric acid (pH <2) and extracted three times with 50 ml of ether each time. The combined organic phases were washed with water, dried over magnesium sulfate, filtered and the solvent removed in vacuo. 4.22 g (13.5 mmol) of 2-hydroxy-4-pyrrolidin-1-yl-2'-carboxybenzophenone were obtained as a solid. M.p .: 203 ° C; λ _max : 355 nm; E ¹ ₁ : 1167.

Example 4

Preparation of 2-hydroxy-4-pyrrolidin-1-yl-2'-methoxycarbonyl benzophenone

1 ml of concentrated sulfuric acid was added dropwise to a solution of 1.32 g (4.2 mmol) of 2-hydroxy-4-pyrrolidin-1-yl-2'-carboxybenzophenone in 40 ml of absolute methanol. The reaction mixture was heated under reflux for 16 h. The solvent was removed in vacuo. The residue was taken up in 100 ml of ethyl acetate, washed with saturated sodium bicarbonate solution and water, dried over sodium sulfate, filtered and the solvent removed in vacuo. The crude product was purified by flash chromatography (mobile phase: pentane / methyl tert-butyl ether 50:50). 1.14 g (3.5 mmol) of 2-hydroxy-4-pyrrolidin-1-yl-2'-methoxycarbonylbenzophenone were obtained. M.p .: 164 ° C; λ _max : 355 nm; E ¹ ₁ : 1179.

Compounds 1 to 8 of Table 2 were prepared analogous to the above examples.

Table 2

Claims (6)

1. Use of amino-substituted hydroxybenzophenones of the general formula I,
in which the variables each have the following meaning independently of one another:
R ¹ , R ^{2 are} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, where R ¹ and R ² together with the nitrogen atom to which they are attached can form a five- or six-membered ring,
R ³ , R ⁴ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ Alkoxycarbonyl, C ₁ -C ₂₀ alkylamino, di (C ₁ -C ₂₀ alkyl) amino, optionally substituted aryl or heteroaryl,
X hydrogen, COOR ⁵ , CONR ⁶ R ⁷ ,
R ⁵ , R ⁶ , R ^{7 are} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, - (YO) _q -Z optionally substituted aryl,
Y - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH (CH ₃ ) -CH ₂ -,
Z -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ ,
m values of 0, 1, 2 or 3,
n values of 0, 1, 2, 3 or 4 and
q integer values from 1 to 20,
as light stabilizers and stabilizers for non-living organic material. 2. Use of compounds according to claim 1, which correspond to the general formula Ia,
in which the variables each have the following meaning independently of one another:
R ¹ , R ^{2 are} hydrogen, C ₁ -C ₁₂ alkyl, where R ¹ and R ² together with the nitrogen atom to which they are attached can form a five- or six-membered ring, and
X is hydrogen or COOR ⁵ and
R ^{5 is} hydrogen, C ₁ -C ₁₂ alkyl or C ₃ -C ₆ cycloalkyl. 3. Use of compounds of formula I according to claim 1 or of the formula Ia as claimed in claim 2 as light stabilizers and Stabilizers for plastics, plastic dispersions, paints or photographic emulsions or layers. 4. Non-living organic material containing compounds of the formula I according to claim 1 or of the formula Ia according to An saying 2 as light stabilizers and stabilizers. 5. Plastics, plastic dispersions, lacquers and photographi emulsions or layers containing compounds of Formula I according to claim 1 or formula Ia according to claim 2 as light stabilizers and stabilizers. 6. Materials according to claims 4 or 5, containing 0.01 to 5 wt .-% of compounds of formula I or Ia each bezo on the total amount of material and compounds of formula I or Ia.