DE2621870A1 - NEW DERIVATIVES OF 4-AMINOPIPERIDINE - Google Patents

Description

CIBA-GEIGY AG, 4002 Basel, Switzerland and SANKYO COMPANY, LIMITED, Tokyo 104, Japan

DR. ERl-ΕΝΠ- Π'ΝΝΕ

Case 3-9915 / MAS 1610/1 + 2

Germany

New derivatives of 4-aminopiperidine

The invention relates to new derivatives of 4-aminopiperidine and their use as stabilizers for organic Polymers against their light degradation.

In US-PS 3,684,765 the stabilization of Polymers described by the addition of derivatives of 4-aminopiperidine. These are derivatives of 4-amino-2,2,6,6-tetramethy! Piperidine the formula

609 851/1103

in which

R represents hydrogen or an acyl group, R-2 represents hydrogen or a monovalent hydrocarbon radical

and
Ro represents hydrogen, an alkoxycarbony group, a mono-, di- or trivalent acyl radical, or a carbamoyl or thiocarbamoyl group.

Similar derivatives of 4-amino-2,2-dimethylpiperidine are described in DT-OS 2 349 962, which deals with the stabilization of polymers.

Derivatives of 4-amino-2,2,6,6-tetraalkylpiperidines which have alkyl groups higher than methyl in the 2-position and in the 3-position Carrying alkyl groups were not previously known.

It has now been found that such higher alkylated 4-aminopiperidine derivatives are valuable stabilizers for organic polymers that are normally exposed to light be dismantled. These new higher alkylated 4-aminopiperidine derivatives correspond to the general formula I,

■ N

R ^J

ι ⁵

^ 3

(D

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and their isomer mixtures or their acid addition salts, in which

R alkyl with 2-6 carbon atoms,

R alkyl with 1-6 carbon atoms,

R alkyl with 1-9 carbon atoms, phenyl, benzyl or phenethyl and

R denotes alkyl with 1-6 carbon atoms, or

4th
R and R together with the C atom to which both are bonded

form a cyclopentyl or cyclohexyl group, R ⁵ alkyl with 1-5 carbon atoms, alkenyl or alkynyl with 3-4 carbon atoms

Atoms or aralkyl with 7-8 carbon atoms, R hydrogen, alkyl with 1-5 carbon atoms, alkenyl or Alkynyl with 3-4 carbon atoms or aralkyl with 7-8 carbon atoms, where

R and R are mutually interchangeable, R ^{7 is} hydrogen, alkyl with 1-12 carbon atoms, cycloalkyl with

5-7 carbon atoms or aralkyl with 7-8 carbon atoms, and when η is 2 and Y is a divalent hydrocarbon radical

7 13

R represents hydrogen or a group -CO-R, wherein R is hydrogen, alkyl with 1-17 carbon atoms, alkenyl with 2-5 carbon atoms, alkoxy with 1-8 carbon atoms, Benzyloxy, cyclohexyloxy, cycloalkyl with 5-7 carbon atoms, phenyl (optionally substituted by chlorine, Lower alkyl, lower alkoxy or hydroxyl), naphthyl, Styryl, aralkyl with 7-8 carbon atoms (optionally

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substituted in the aromatic radical) or a monovalent heterocyclic radical,
X hydrogen, an oxyl radical,

Alkyl with 1-8 carbon atoms, alkenyl with 3-6 carbon atoms, alkoxyalkyl with 2-21 carbon atoms, aralkyl with 7-8 carbon atoms, its aromatic radical with chlorine, hydroxyl, alkyl with 1-4 carbon atoms or alkoxy can be substituted by 1-8 carbon atoms, furthermore X is a 2,3-epoxypropyl group, a aliphatic acyl group with 1-12 carbon atoms or one of the

Groups -CH ₂ COOR ⁸ , -CH ₂ CH (R ⁹ ) -OR ¹⁰ , -COOR ¹¹ or

V)
-CONHR means in which

R ⁸ alkyl with 1-8 carbon atoms, alkenyl with 3-6 carbon atoms, phenyl, aralkyl with 7-8 carbon atoms or cyclohexyl,

R hydrogen, methyl or phenyl,

R is hydrogen or an aliphatic, aromatic, araliphatic or alicyclic acyl group with up to 18 carbon atoms, the aryl radical of which with chlorine, alkyl with 1-4 carbon atoms, Alkoxy with 1-8 carbon atoms and / or hydroxyl can be substituted,

R is alkyl with 1-8 carbon atoms, phenyl, benzyl or cyclohexyl and

R alkyl with 1-12 carbon atoms, aryl with 6-10 carbon atoms (das can be substituted by chlorine or lower alkyl), aralkyl with 7-8 carbon atoms or cyclohexyl,

η is 1, 2 or 3,

and when η is 1, 609851/1103

262 1U7Ü

13th

Y is hydrogen or one of the groups -CO-R,

_R 15

-CO-NR ¹⁴ , -SO ₂ -R ¹⁶ , -P (R ²⁰ ) ₂ , -P (O) (R ^2O ) ₂ , -P (S) (R ²⁰ ) ₂ , -CO-R ¹⁷ -COOH or -C0-R ¹⁷ -C00Me, where R is hydrogen, alkyl with 1-17 carbon atoms, alkenyl with 2-5 carbon atoms, alkoxy with 1-8 carbon atoms, benzyloxy, cyclohexyloxy, cycloalkyl with 5-7 Carbon atoms, phenyl (optionally substituted by chlorine, lower alkyl, lower alkoxy or hydroxyl), naphthyl, styryl, aralkyl with 7-8 carbon atoms (optionally substituted in the aromatic radical) or a monovalent heterocyclic radical,

14th
R is hydrogen or alkyl with 1-4 carbon atoms, R is hydrogen or alkyl with 1-18 carbon atoms, aryl with 6-10 carbon atoms (optionally substituted with chlorine or lower alkyl), aralkyl with 7-8 carbon atoms or Mean cyclohexyl, or

R "* and R together with the N atom to which they are bound, form a piperidine, pyrrolidine or morpholine ring,

R methyl, ethyl, phenyl, tolyl, naphthyl or tetrahydronaphthyl,

R ¹⁷ -CH ₀ CH ₀ -, -CH = CH-, - (CH ₉ ) ~ - or o-phenylene,

20th
R alkoxy with 1-12 carbon atoms, aryloxy with 6-12 carbon atoms, alkyl with 1-12 carbon atoms, aryl with 6-14 carbon atoms, aralkyl

20 with 7-8 carbon atoms or cyclohexyl and R in an aromatic radical can also be substituted

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"""HM-

by alkyl with 1-4 carbon atoms and / or hydroxyl and Me the equivalent of a salt-forming mono- to tetravalent Is metal cation, or

Y and R together with the N atom to which they are attached

a succinimide, maleimide or phthalimide ring form, and

if η is 2,

18th

Y one of the groups -CO-, -COCO-, -CO-R-CO-,

IQ "ν 9Π \ or» \ on -CONH-R-NHCO-, ^ PR, / P (O) R ^ZU or ^ P (S) R ^ZU , where

R alkylene with 1-10 carbon atoms, alkenylene with 2-4 carbon atoms, thiaalkenylene with one S and 2-4 carbon atoms, arylene with 6-12 carbon atoms or cyclohexylene,

R alkylene with 2-10 carbon atoms, arylene with 6-13 carbon atoms or Is cyclohexylene,

7 13

and when R is hydrogen or -CO-R ',

Y can also be alkylene with 2-10 carbon atoms, arylene with 6-12 carbon atoms, meta- or para-xylylene or 1,4-cyclohexylene,

and if η is 3,

Y is a benzene-tricarbonyl radical, a 1,3,5-triazine-2,4,6-triyl radical or ~ P, ^ "is PO or ^ PS.

R, R and R ⁺ can be straight or branched-chain groups with 2-6 carbon atoms, such as, for example, ethyl, propyl, butyl, isobutyl, isopentyl or n-hexyl; R and R can also be methyl.

609851/1 103

R can be a straight or branched chain alkyl group with 1-9 carbon atoms such as methyl, ethyl, propyl, η-butyl, isobutyl, isopentyl, n-hexyl, 2-ethylhexyl, n-nonyl or isononyl.

R and R can be alkyl groups with up to 5 carbon atoms, such as methyl, ethyl, isopropyl, isobutyl, n-pentyl. Before-

5 1

preferably R contains one C atom less than R, and

R ^{6 is} one carbon atom less than R ² , where R and R are below. can be interchangeable. R and R can furthermore be alkenyl or alkynyl groups, for example allyl, methallyl, 2-butenyl or propargyl, but preferably allyl. R and R can also be aralkyl groups, such as benzyl, phenylethyl or methylbenzyl, but preferably benzyl.

If R is alkyl with up to 12 carbon atoms, it is preferably a straight-chain alkyl group such as methyl, ethyl, Propyl, η-butyl, n-pentyl, n-hexyl, n-decyl or n-dodecyl. When R is aralkyl, it can be benzyl, phenylethyl or methylbenzyl, and it is preferably benzyl. When R Cycloalkyl can be cyclopentyl, cyclohexyl or a methyl derivative thereof, but preferably cyclohexyl. R is particularly preferably hydrogen.

If X is an alkyl group with 1-8 carbon atoms, this can be, for example, methyl, ethyl, n-propyl, η-butyl, n-hexyl or be n-octyl, but preferably alkyl with 1-4 carbon atoms,

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especially methyl.

If X is an AJ.kenyl group with 3-6 carbon atoms, then can this can be, for example, allyl, 2-butenyl or 2-hexenyl; preferably it is an alkenyl group with 3-4 carbon atoms and particularly preferably allyl.

If X is an alkoxyalkyl group with 2-21 C atoms, its alkyl part can have 1-3 C atoms and the alkoxy part 1-18 carbon atoms, for example X can then e.g. 2-methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, methoxymethyl, 3-n-butoxypropyl, 2-octoxyethyl, 2-dodecyloxyethyl or 2-octadecyloxyethyl, preferably an alkoxyalkyl group with 2-6 carbon atoms.

When X is an aralkyl group with 7-8 C atoms, which is im aromatic moiety can be substituted, so this can e.g. u.-inzyl, phenylethyl, o-, m- or p-chlorobenzyl, o-, m- or r ... methylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl, p-methoxy ~, p-n-butoxy ~ or p-octoxybenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl be, preferably benzyl.

O O

If X is a group of the formula -CH ₂ COOR, R can be alkyl with 1-8 C atoms, such as, for example, methyl, ethyl, isopropyl, η-butyl, isobutyl, tert-butyl, isopentyl or

Octyl, or R is alkenyl with 3-6 carbon atoms, such as allyl,

2-butenyl or 2-hexenyl, or R is a phenyl group or an aralkyl group with 7-8 carbon atoms, such as benzyl or

Phenylethyl, or a cyclohexyl group; R is preferably an alkyl group with 1-4 C atoms. 609851/1103

q in If X is a group of the formula -CH ₂ -CH (R) -OR, then can

R can be hydrogen, methyl or phenyl, preferably hydrogen, and R can be hydrogen or an aliphatic, aromatic, araliphatic or alicyclic acyl group with up to 18 carbon atoms, for example acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl, acrylic, Benzoyl, chlorobenzoyl, toluyl, isopropylbenzoyl, 2,4-dichlorobenzoyl, 4-methoxybenzoyl, 3-butoxybenzoyl, 2-hydroxybenzoyl, 3,5-di-tert-butyl-4-hydroxybenzoyl-, β (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl, phenylacetyl, Cinnamoyl, hexahydrobenzoyl, 1- or 2-naphthoyl or decahydronaphthoyl group.

If X is an aliphatic acyl group with up to 12 carbon atoms, this can be an alkanoyl or alkenoyl group such as formyl, acetyl, acrylic, crotonyl, capryloyl or lauroyl.

11 11

If X is a group of the formula -COOR, then R can be an alkyl group with 1-8 C atoms, e.g. methyl, ethyl, isobutyl or octyl, a phenyl group, a benzyl group or a cyclohexyl group.

12 12

If X is a group -CONHR, then R can be an alkyl group with 1-12 C atoms, e.g. methyl, ethyl, n-propyl, n-butyl, Dodecyl or 2-ethylhexyl; or an aryl group with 6-10 carbon atoms, which can be substituted by chlorine or

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Alkyl having 1-4 carbon atoms, for example phenyl, ο-, m- or p-chlorophenyl, o-, m- or p-tolyl or α- or ß-naphthyl; or an aralkyl group with 7-8 C atoms, e.g. benzyl or phenylethyl; or a cyclohexyl group.

13 13 If η is 1, then Y can be a group -CO-R and R can Be hydrogen or an alkyl group with 1-17 carbon atoms, such as methyl, ethyl, n- or isopropyl, n- or tert-butyl, n- or Isopentyl, 1-ethylpentyl, nonyl, undecyl, pentadecyl or Heptadecyl; or an alkenyl group with 2-5 C atoms, such as vinyl, 1-propenyl, 2-methyl-1-propenyl, isopropenyl or 1,3-pentadienyl; or an alkoxy group with 1-8 carbon atoms, such as methoxy, ethoxy, butoxy or octoxy; or a benzyloxy group, cyclohexyloxy group or cycloalkyl group with 5-7 carbon atoms, e.g. cyclopentyl, cyclohexyl or methylcyclohexyl; a phenyl group which can be substituted by chlorine, alkyl with 1-4 carbon atoms, alkoxy with 1-4 carbon atoms or hydroxyl, such as e.g. o ~, nw or p-chlorophenyl, o-, m- or p-methyl-, p-isopropyl or p ~ tert-butylphenyl, m- or p-methoxy- or p-n-butoxyphenyl, o-hydroxyphenyl, 2-hydroxy-3- or 4-methy! phenyl or 3,5-di-tert-butyl-4-hydroxyphenyl; or a naphthyl or styryl group; or an aralkyl group with 7-8 carbon atoms, which Im aromatic moiety can be substituted as explained above for phenyl, for example benzyl, phenylethyl or 3,5-di-tert-butyl-4-hydroxyphenylethyl; or a monovalent heterocyclic group, such as 2-, 3- or 4-pyridyl, 2-furyl or 2-thienyl.

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R ¹⁵ If Y is a group of the formula -CON-R, then R can be hydrogen or lower alkyl and R can be hydrogen or alkyl with 1-18 carbon atoms, such as methyl, ethyl, n-propyl, η-butyl, Dodecyl, 2-ethylhexyl, n-hexadecyl or n-octadecyl; or an aryl group with 6-10 carbon atoms which can be substituted by chlorine or lower alkyl, such as, for example, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-tolyl or cc- or ß-naphthyl ; or an aralkyl group with 7-8 carbon atoms, such as benzyl or phenylethyl; or a cyclo-

14 15
hexyl group; or R and R ″ together with the N atom to which they are attached form a piperidine, pyrrolidine or morpholine ring. Particularly preferred groups

R ¹⁵
-CON-R ¹⁴ are those of the formula -CONHR ¹⁵ (where R ^{15 is} the above

has given meaning).

If Y. is a group of the formula -CO-R-COOMe, then means Me is the equivalent of a salt-forming cation such as Na, Ba, Ni, Ca, Zn, Co or Sn.

18 If η is 2, then Y can be a diacyl group -CO-R -CO-,

18th
where R can be alkylene with 1-10 carbon atoms, such as

Methylene, ethylene, tetramethylene, hexamethylene, octamethylene or decamethylene; or a thiaalkylene group with one S and 2-4 carbon atoms, such as, for example, 2-thiapropylene-1,3 or 3-thiapentylene-1,5; or an alkenyl group with 2-4 carbon atoms, such as

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CH ₀

Ii ²

for example vinylene, 2-butenylene or -CH ₂ -C-; or an arylene group with 6-12 carbon atoms, such as ο-, m- or p-phenylene,

18 1,4-naphthylene or 4,4'-diphenylene; or R is one Cyclohexyl group e.

19th

If X is a group of the formula -CONH-R -NHCO-, R can be an alkylene group with 2-10 C atoms, such as, for example, ethylene, tetramethylene, hexamethylene or decamethylene; or an arylene or methylarylene group with 6-13 carbon atoms, such as, for example, o ~, m- or p-phenylene, 2,4-tolylene, 1,5-naphthylene, 4,4'-diphenylene, 4,4'-diphenylene or 4,4 ¹ -diphenylene oxide;

• 19th
or R is a cyclohexylene group such as 1,4-cyclohexylene.

7 13

If R is hydrogen or an acyl group -CO-R, then Y can also be an alkylene group and 2-10 C atoms, such as, for example, a ri, tri, tetra, hexa, octa or decamethylene radical, or ο. · 1 · ΐ & arylene group, ie sB phenylene, naphthylene or diphenylene.

If η is 3, then Y can be a benzene-tricarbonyl radical, such as, for example, the trivalent acyl radical of trimellitic or trimesic acid.

The present invention is also intended to encompass the acid addition salts of the compounds of the formula I. Acids that form such addition salts can be, for example, inorganic acids,

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such as sulfuric acid, hydrochloric acid or phosphoric acid; or organic carboxylic acids such as formic, acetic, valeric, Stearic, oxalic, adipic, sebacic, maleic, benzoin, 4-tert. Butylbenzoic, 3,5-di-tert-butyl-4-hydroxybenzoic, salicylic or terephthalic acid e $. or sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid; or containing phosphorus organic acids such as diphenylphosphoric acid or phenylphosphonic acid.

The 4-aminopiperidine derivatives of the general formula I have asymmetrical carbon atoms. Accordingly “Mixtures of these isomers” does not only mean the mixtures of the positional isomers in the 3- and 5-positions, but rather also the different types of stereoisomers. The 4-oxopiperidine derivatives used as starting material are already mostly isomer mixtures, which before their implementation or at each of the following synthesis stages by the customary methods of Isomer separation can be separated.

Particular preference is given to compounds of the formula I in which R and R are ethyl groups, R, R and R are methyl groups, and R is hydrogen and R represent hydrogen or methyl, and X either hydrogen or an oxyl radical, a methyl group, Allyl group, benzyl group, an acetyl, acrylic or cro

O Q

tonyl radical, a group -CH ₂ COOR (where R is lower alkyl) or a group -CHL-CH ^ OR (where R is hydrogen, a

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an alphatic acyl group with 1-4 C atoms or a benzoyl group is), where X is particularly preferably hydrogen or methyl, and η is 1 or 2 and in the case of

13 13

n »l Y a group -CO-R (where R is an alkyl group with

1-17 carbon atoms, a phenyl group which can be substituted by up to three identical or different lower alkyl groups and / or hydroxyl groups) or a group -SO ₂ R ¹⁶ (where R ^{16 is} methyl, phenyl or tolyl) or a group - CONH-R is (where R is an alkyl group with 1-12 C atoms, a phenyl or a cyclohexyl group

represents) and in the case of n = 2 Y a group -CO-, -COCO-

18 18

or -CO-R -CO- is where R is an alkylene group having 1-10 C atoms or a phenylene group, or Y is a Represents group -CONH-R-NHCO-, in which R is hexamethylene, Is 2,4-tolylene or 4,4'-diphenylenemethane.

Examples of individual 4-aminopiperidine derivatives of the formula I. are given in the following list, but this does not limit the invention to the compounds mentioned should mean.

4-acetamido-2,6-diethyl-2,3,6-trimethyl piperidine 4-lauroylamido-2,6-diethyl-2,3,6-trimethylpiperidine 4-stearamido-2,6-diethyl-2,3,6-trimethylpiperidine 4-acrylamido-2,6-diethyl-2,3,6-trimethyl piperidine 4-methacrylamido-2,6-diethyl-2,3,6-trimethyl piperidine

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4-Crotoriamido-2,6-diethyl-2,3,6-triraethy! Piperidine 4 ~ phenylacetamido-2,6-diethyl-2,3,6-trimethylpiperidine 4-cyclohexanecarbonaraido-2,6-diethyl-2,3,6-trimethylpiperidine 4 ~ benzamido-2,6-diethyl ~ 2,3,6-trimethylpiperidine 4-Benzamido-2,6-diethyl-1,2,3,6-tetramethylpiperidine 4-Benzamido-2,6-diethyl-2,3,6-trimethylpiperidine-1-oxyl 4-p-chlorobenzamido-2,6-diethyl-2,3,6-trimethylpiperidine 4-p-toluamido-2,6-diethyl-2,3,6-trimethyl piperidine 4-o-Toluamido-2,6-diethyl-2,3,6-trimethylpiperidine 4-ß-Naphtharaido ~ 2,6-diethyl-2,3,6-trimethylpiperidine 4- (2-furancarbonamido) -2,6-diethyl-2,3,6-trimethylpiperidine 4-ureido-2,6-diethyl-2,3,6-trimethylpiperidine 4- (3 ~ ethylureido) -2,6-diethyl-2,3,6-trimethylpiperidine 4- (3-Benzylureido) -2,6-diethyl-2,3,6-trimethylpiperidine 4- (3-Cycohexylureido) -2,6-diethyl-2,3,6-trimethylpiperidine 4_ (3_Phenylureido) -2,6-diethyl-2,3,6-trimethylpiperidine 4- (3-Phenylureido) -2,6-diethyl-1,2,3,6-tetramethylpiperidine 4- (3-stearylureido) -2,6-diethyl-2,3,6-trimethylpiperidine 4- (3,3-dimethylureido) -2,6-diethyl-2,3,6-trimethylpiperidine 4-methanesulfonamido-2,6-diethyl-2,3,6-trimethylpiperidine 4-benzenesulfonamido-2,6-diethyl-2,3,6-trimethylpiperidine 4-p-Toluenesulfonamido-2,6-diethyl-2,3,6-trimethylpiperidine 4-amino-2,6-diethyl-2,3,6-trimethylpiperidine 4-methylamino-2,6-diethyl-2,3,6-trimethylpiperidine 4-caprylamido-2,6-diethyl-2,3,6-trimethylpiperidine 4-Cyclohexylamino-2,6-diethyl-2,3,6-trimethylpiperidine

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4-Benzylamino-2,6-diethyl-2,3,6-trimethylpiperidine 4- (N-methylacetamido) -2,6-diethyl-2,3,6-trimethylpiperidine 4- (N-methylbenzamido) -2 , 6-diethyl-2,3,6-trimethylpiperidine 4- (N-cyclohexylbenzamido) -2,6-diethyl-2,3,6-trimethylpiperidine 4- (N-benzylbenzamido) -2,6-diethyl-2,3 , 6-trimethylpiperidine 4-acetamido-1-butyl-2,6-diethyi-2,3,6-trimethylpiperidine 4-benzamido-1-allyl-2,6-diethyl-2,3,6-trimethy! Piperidine 4- Acetamido-l-benzyl-2,6-diethyl-2,3,6-trimethylpiperidine 1,3-bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) urea N ₅ N ¹ - bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) oxalamide N, N'-bis (2,6-diethyl-l, 2, 3,6-tetramethyl-4-piperidyl) oxalamide N , N ^f -Bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) succinamide N, N ¹ -Bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) adipamide N, N ¹ -bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) -sebacamide N, N ^f -bis (2,6-diethyl-2,3,6-trimethyl-4 -piperidyl) -fumaramide N, N'-bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) -terephthal-

1,6-bis [3- (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) ureido] -n-hexane

p, p ^! -Bis [3- (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) ureido] -diphenylmethane

2,4-bis [3- (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) ureido] toluene

1,5-bist3- (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) ureido] naphthalene

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p, p ^f -Bis [3- (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) ureido] diphenyl oxide

1,6-bis [3- (2,6-diethyl-1,2,3,6-tetramethyl-4-piperidyl) ureido] -n-hexane

4-amino-2,2,6,6-tetraethyl-3,5-dimethylpiperidine 4-methylamino-2,2,6,6-tetraethyl-3,5-dimethylpiperidine 4-acetamido-2,2,6,6-tetraethyl-3,5-dimethylpiperidine 4-benzamido-2,2,6,6-tetraethyl-3,5-dimethylpiperidine 4-Benzamido-2,2,6,6-tetraethyl-1,3,5-trimethylpiperidine 4- (3-Phenylureido) -2,6-diethyl-2,3,6-trimethylpiperidine-1-oxyl 4-Benzamido-2,2,6,6-tetraethyl-3,5-dimethylpiperidin-1-oxyl 4- (N-Methylacetamido) -2,2,6,6-tetraethyl-3,5-dimethylpiperidine

4- (N-methylbenzamido) -2,2,6,6-tetraethyl-3,5-dimethylpiperidine

4-amino-2,6-dipropyl-2,6-dimethyl-3-ethylpiperidine 4-methylamino-2,6-dipropyl-2,6-dimethyl-3-ethylpiperidine, 4-acetamido-2,6-dipropyl-2,6-dimethyl-3-ethylpiperidine 4-Benzamido-2,6-dipropyl-2,6-dimethyl-3-ethylpiperidine 4-Benzamido-2,6-dipropyl-1,2,6-trimethyl-3-ethylpiperidine 4- (N-methylbenzamido) -2,6-dipropyl-2,6-dimethyl-3-ethylpiperidine

N, N'-bis (2,6-dipropyl-2,6-dimethyl-3-ethyl-4-piperidyl) oxalamide
4-butylamino-2,6-diethyl-2,3,6-trimethylpiperidine

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4-octylamino-2,6-diethyl-2,3,6-trimethy! Piperidine 4-dodecylamino-2,6-diethyl-2,3,6-trimethy! Piperidine 4- (N-butylbenzamido) -2,6- diethyl-2,3,6-trimethylpiperidine 4- (N-octylacetamido) -2,6-diethyl-2,3,6-trimethylpiperidine 4- (N-octylbenzamido) -2,6-diethyl-2,3,6- trimethylpiperidine 4- (N-dodecyl-acetamido) -2j6-diethyl-2,3,6-trimethylpiperidine 4- (N-dodecylbenzamido) -2,6-diethyl-2,3,6-trimethylpiperidine N, N ^f -Bis- (2 _J 6-diethyl-2,3,6-trimethyl-4-piperidyl) -N, N ^l dibutyl-oxalamide

N _> N ^f -Bis (2 _} 6-diethyl-2,3,6-trimethyl-4 »piperidyl) ^ N, N ^t dioctyl oxalamide

N, N ^I -Bis (2 ₎ 6-diethyl-2 _> 3 _J 6-trimethyl-4-piperidyl) -N _J N'-didodecyl-oxalamide

N, N'-bis (2 ₃ 6-diethyl-2,3,6-trirriethyl-4-piperidyl) -N, N ^l dibutyl-adipamide

N, N ^I -Bis- (2,6-diethyl-2,3 _J 6-trimethyl-4-piperidyl) -N, N'-dioctyl-sebacamide

N, N ¹ -Bis- (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) -N, N ¹ -dibutyl-terephthalamide

N, N'-bis (2 _} 6-diethyl-2,3 _J 6-trimethyl-4-piperidyl) -N _> N ^I -dioctyl-isophthalamide

1,3-bis (2,6-diethyl-2,3 ₎ 6-trimethyl-4-piperidyl) -l, 3-dibutyl urea

1,3-bis- (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) ~ 1,3-dioctyl urea

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1,3-bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) -1,3-didodecylurea

N, N ¹ -bis- (2,6-diethyl ~ 2 _} 3,6-trimethyl-4-piperidyl) -ethylenediamine

N, N ¹ -bis- (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) -hexamethylenediamine

N, N ^l -Bis- (2 _} 6-diethyl-2,3,6-trimethyl-4-piperidyl) -N _J N ^l diacetylethylenediamine

N _> N'-bis (2,6-diethyl-2,3 _J 6-trimethyl-4-piperidyl) -N, N ^I -dibenzoylethylenediamine

N _s N ^I -Bis- (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) -N, N ^t diacetylhexamethylenediamine

N, N'-bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) -N, N ¹ -diben2oy! Hexamethylenediamine

4-Amino-2,6-diisobutyl-2,6-dimethyl-3-isopropylipiperidine 4-methylamino-2,6-diisobutyl-2,6-dimethyl-3-isopropylpiperidine 4-acetamido-2,6-diisobutyl-2,6-dimethyl-3-isopropylpiperidine 4-Benzamido-2,6-diisobutyl-2,6-dimethyl-3-isopropylpiperidine 4- (N-Methylbenzamido) -2,6-diisobutyl-2,6-dimethyl-3-isopropylp ip er id in

4- (N-Methylbenzamido) -2,6-diisobutyl-1,2,6-trimethyl-3-isopropylpiperidine

4-amino-2,6-diisopentyl-2,6-dimethyl-3-isobutylpiperidine 4 ~ methylamino-2,6-diisopentyl-2,6-dimethyl-3-isobutyl - '* piperidine

609851/1103

4-Acetamido-2,6-diisopentyl-2j6-diiuethyl-3-isobutylpiperidine 4-3enzamido-2j6-diisopentyl-2 _s 6-dimethyl-3-isobutylpiperidine 4-3enzamido-2,6-diisopentyl-1,3,6- trimethyl-3-isobutylp ip er id in

4- (N-Methylbenzamido) -2 _s 6-diisopentyI-lj2j6-trimethyl-3-isobutyipiperidine

N _s N ^f -Bis (2,6-diisopentyl-2,6-dimethyl-3-isobutyl-4-piperidyl).

oxalamide

4-Benzamido-2,6-diisopentyl-2 _s 6-dimethyl-3-isobutylpiperidin-1-oxyl

4-Amino-2-nonyl-6-ethyl-2,3,6-trimethylpiperidine 4-acetamido-2-nonyl-6-ethyl-2,3,6-trimethylpiperidine 4-3enzamido-2-nonyl-6 ~ ethyl-1,2 _s 3,6-tetramethy! piperidine 4-amino-2,2-di-n-butyl-6-ethyl-3,6-dimethy! piperidine 4-acetamido-2,2-di-n- butyi-6-ethyl-3,6-dimethyl-piperidine 4-Aπlino-2-phenylethyl-6-ethyl-2,3,6-triraethyl-piperidine 4-benzamido-2-phenylethyl-6-ethyl-2p 3,6 trimethyl piperidine 2,4,6-tris (2,6-diethyl-2,3,6-trimethylpiperidinyl-4-amino) -1,3,5-triazine

2,4,6-tris (2,6-diethyl-1,2,3,6-tetramethylpiperidinyl-4-amino) -1,3,5-triazine

2,4,6-Tr is (2,6-diethyl-2,3,6-triπlethyl-1-oxylpiρeridinyl-4- amino) 1,3,5-triazine

2, 4,6-tris (2,2,6, 6-tetraethyl-3,5-diraethylpiperidinyl-4-amino) -1,3,5-triazine

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2,4,6-tris (2,6-dipropyl-2,6-dimethyl-3-ethylpiperidinyl-4-amino) 1,3,5-triazine

2,4,6-tris (2,6-diisobutyl-2,6-dimethyl-3-isopropylpiperidinyl-4-amino) 1,3,5-triazine

2,4,6-tris (2,6-diisopentyl-2,6-dimethyl-3-isobutylpiperidinyl-4-amino) -1,3,5-triazine

1-acetyl-2,6-diethyl-2,3,6-trimethyl-4-acetamidopiperidine 1-acryloyl-2,6-diethyl-2,3,6-trimethyl-4-acrylamidopiperidine l-crotonyl-2,6-diethyl-2,3,6-trimethyl-4-crotonamidopiperidine 1 «acetyl-2,6-diethyl-2,3,6-trimethyl-4-benzaiaidopiperidine l-capryloyl-2,6-diethyl-2,3,6-trimethyl-4-benzamidopiperidine l-Lauroyl-2,6-diethyl-2,3,6-trimethyl-4-benzamidopiperidine N, N'-bis (1-acetyl-2,6-diethyl-2,3,6-triraethyl-4-piperidyl) oxalarid

4-Ethosycarbonaiaido-2,6-diethyl-2,3,6-trimethy! Piperidine 4-Benzyloxycarbonamido-2,6-diethyl-2,3,6-trimethylpiperidine 1-asthoxycarbonyl-2,6-diethyl-2,3,6-trimethyl-4-ethoxycarbonamidopiperidine

l-Benzyloxycarbonyl ^ ö -diethyl ^^ so-trmethyl ^ -benzyloxycarbonamidopiperidine

1-ethoxycarbonylmethyl-2,6-diethyl-2 ₅ 3,6-trimethyl-4-benzamidopiperidine

1-Benzoyloxyethyl-2,6-diethyl-2,3,6-trimethyl-4-acetamidopiperidine

l-ethoxyethyl-2,6-diethyl-2,3,6-trimethyl-4-acetamidopiperidine

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4- (3,5-Di-tert-butyl-4-hydroxybenzamido) -2,6-diethyl-2,3,6-trim thy! piperidine

4- [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] -2,6-diethyl-2,3,6-tr imethy! piperidine

Diphenyl- (2,6-diethyl-2,3,6-trimethyl-4-piperidylamino) -phos phine

Phenyl bis (2,6-diethyl-2,3,6-trimethyl-4-piperidylamino) phosphine oxides

O, O ~ bis (4-tert-butyl-phenyl) -2,6-diethyl-2,3,6-trimethyl-4-p ip er idylamino-thiopho sphat

O, O-bis (4-tert-butylphenyl) -2,6-diäthyi-2,3 _J 6-trimethyl-4-piperidylaraino-phosphate

Tris (2,6-diethyl-2,3,6-trimethyl-4-piperidylamino) phosphine Tris (2,6-diethyl-2,3,6-trimethyl-4-piperidylamino) phosphine ox id.

The 4-aminopiperidine derivatives of the formula I can be different Ways to be prepared using the types of reactions that are common to the preparation of amines and Amine derivatives are known. Depending on the type of compound of the formula I, a suitable type of reaction must be used can be selected as described in the following example:

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i) Compounds of the formula I in which R and Y are hydrogen or Y is hydrogen and R is alkyl or cycloalkyl can be prepared by catalytic hydrogenation of the corresponding 4-oxopiperidines II in the presence of ammonia or a primary amine:

II

Suitable catalysts are, for example, Raney nickel, palladium on carbon or platinum oxide. The hydrogenation is preferably carried out in organic solvents, for example in methanol, ethanol or dioxane.

The 4-oxopiperidines of the formula II can be prepared by reacting an aliphatic ketone, which is a higher homologue of acetone, with ammonia. For example, 2,3,6-trimethyl-2,6-diethyl-4-oxopiperidine is prepared from methyl ethyl ketone and ammonia as described by W.Traub in Chem. Reports j41 (1908), 777 .

Another method is the hydrolysis of alkyl-substituted tetrahydropyrimidines in the presence of acidic catalysts, for example analogous to the process of US Pat. No. 3,513,170.

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Compounds of the formula II which are different in the 2- and 6-positions Having substituents are accessible by reaction of one

1 2
Ketones R -CO-R with NIL, and hydrolysis of the pyri

amine derivatives to the aminoketone of the formula R ² R ⁶

R ₁ -C-CH-CO-CH ₀ R ⁵
1 j 2

NH ₂
as described in HeIv.Chim.Acta JK) (1947), 1114, and subsequent reaction of the aminoketone with ammonia and

3 4
a second ketone R -CO-R with the formation of another piperidine derivative, as inmonths. Chemie J38 (1957), 464, and subsequent hydrolysis of the pyrimidine derivative to the piperidone derivative.

Such and similar processes for the preparation of alkylated 4-piperidones are also in DT-OS 2 429 745, 2,429,746, 2,429,935, 2,429,936 and 2,429,937.

Compounds of the formula II in which R or R is hydrogen can be substituted in these positions by reacting with a secondary amine and reacting the enamine formed with a reactive organic halogen compound such as allyl bromide or benzyl chloride, thereby forming a compound

5 6 of the formula II is obtained in which R or R is allyl or benzyl or a similar substituent.

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13th

2) Compounds of the formula I in which Y is an acyl radical -COR,

18th
-COCO-, -CO-R -CO- or a benzenetricarbonyl radical can be prepared by acylation of III using the corresponding carboxylic acids or dicarboxylic acids, or their anhydrides, esters or halides according to the usual methods for acylating primary or secondary Amines.

3) Compounds of the formula I in which Y is a carbamoyl group

-CO-NH-R ¹² or -CONH-R ¹⁹ -NHCO- can be selected from the amines

12th

of formula III by reaction with isocyanates R NCO or

19th
Diisocyanates OCN-R -NCO are produced.

4) Compounds of the formula I in which η 2 and Y is -CO- or η 1 and Y is -CONBu _s can be prepared by reacting the amines of the formula III with urea or carbamic acid atom.

5) Compounds of the formula I in which Y is a carbamoyl group -CO-N (R ¹⁴ ) (R ¹⁵ ) and both R ¹⁴ and R ^{15 are} hydrocarbon radicals or form a ring together with the N atom can be converted from the amines III by Reaction with chlorine

• j ff 1 £ -

carbamates of the formula Cl-CO-N (R) (R) are produced.

16

6) If Y represents a SuIfony! Group -SO ₂ -R, so can

the compounds of formula I from those of formula III by reaction with a sulfonic acid chloride, for example p-toluenesulfonyl chloride.

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OQ

7) If Y is a phosphorus-containing group of the formula -P (R) " _s -P (O) (R ^2O ) ₂ , -P (S) (R ²⁰ ) ,,,> PR ²⁰ ,) P (O) R ^2O ₎ -) P (S) R ^2O , -) P ₎ ^ or "T-PS, these groups can be introduced by reacting the amines III with the corresponding phosphorus chlorides ClP (R ²⁰ ) ₂ , ClP (O) (R ²⁰ ) _£ , ClP (S) (R ²⁰ ) _£ ,

9Ω 9Ω 9Π

R ^ ^U PC1 ₂ , R ^TO P (O) Cl ₂ , R ^ ¹ T (S) Cl ₂ , PCl ₃ , POCl ₃ or PSCl ₃ .

17 S) Compounds of the formula I in which Y is -CO-R-COOH can by reacting the amines III with cyclic dicarboxylic acid anhydrides, such as maleimide, succinimide or phthalic anhydride can be obtained. Is in the initial connection III R is hydrogen, this reaction can be used to obtain compounds of the formula I in which Y and R 'are taken together and the N atom form a cyclic imide ring.

9) The metal salts where Y is -CO-R-COOMe are selected from

free acids obtainable by neutralization, for example with a suitable metal carbonate or hydroxide.

10) Compounds of the formula I in which X is a hydrocarbon radical can be prepared from the corresponding compounds, in which X is hydrogen, by customary substitution reactions be prepared, for example by reaction with dimethyl sulfate, allyl chloride or bensyl bromide. In analog Way, the nitroxyls (formula I, X = O) from the compounds with X = H by reaction with percarboxylic acids, for example with 3-chloroperbenzoic acid, or with hydrogen

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peroxide in the presence of catalysts such as sodium tungstate, Alternatively, the N-substitution can also be carried out on the piperidones of the formula II are followed by the 4-amination and other reactions.

12) Compounds in which X is -CH ₂ -CH (R ⁹ ) -OH can be obtained from the compounds where X «= H by reaction with alkylene oxides, for example ethylene oxide, propylene oxide or styrene oxide. In a subsequent acylation stage, these compounds can be converted into compounds in which

X is -CH ₂ CH (R) -OR ¹⁰ and R ^{10 is} an acyl group. If epichlorohydrin is used as alkylene oxide, a chlorohydrin compound is obtained which can be converted into the corresponding N-glycidyl compound by alkaline treatment.

13) Compounds in which X is an acyl group can be obtained from the corresponding NH compounds by acylation with carboxylic acid chlorides, esters or anhydrides are obtained. When η is 1, reaction 13) can be combined with Reaction 2) with simultaneous acylation on the ring nitrogen and on the 4-amino group.

609851/1103 '

262Ί870

11 14) Compounds in which X is a group -COOR can be obtained from the corresponding NH compounds by Reaction with chlorocarbonates GlCOOR.

15) Acid addition salts of the compounds of the formula I can be prepared by neutralizing the piperidine derivatives with the corresponding acids, preferably in an organic solvent or its mixture with water. Salt formation is not possible if X and Y or X and R are acyl groups or when Y is -CO-R -COOMe.

16) Compounds of the formula I in which η is 2, Y is a divalent hydrocarbon radical and R is hydrogen, can be obtained from the 4-oxopiperidines of the formula II by catalytic hydrogenation in the presence of an equivalent amount of the corresponding diamine. The corresponding acyl derivatives (R ⁷ --CO-R ¹³ ) can be obtained from these products by reaction with R ¹³ COCl or (R ¹³ CO) ₂ O.

According to the invention it was found that 4-aminopiperidine derivatives of formula I and their acid addition salts a large number of organic polymers against light damage can stabilize and have excellent compatibility with these polymers. Polymers, which such can be stabilized are:

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1. Polymers of mono- and diolefins, for example polyethylene (which can optionally be crosslinked), polypropylene, Polyisobutylene, polymethylbutene-1, polymethylpentene-1, Polyisoprene or polybutadiene.

2. Mixtures of the polymers mentioned under 1), e.g. mixtures of polypropylene with polyethylene or with Polyisobutylene.

3. Copolymers of mono- and diolefins, such as ethylene-propylene copolymers, Propylene-butene-1 copolymers, propylene-isobutylene copolymers, Ethylene-butene-1 copolymers and terpolymers of ethylene with propylene and a diene, such as Hexadiene, dicyclopentadiene or ethylidene norbornene.

4. Polystyrene.

5. Copolymers of styrene or α-methylstyrene, such as styrene-butadiene, Styrene-acrylonitrile, systyrene-acrylonitrile-methyl acrylate; Mixtures of high impact strength made from styrene copolymers and another polymer such as a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene or Styrene-ethylene / butylene-styrene.

6. Graft or graft copolymers of styrene, such as styrene

on polybutadiene, styrene and acrylonitrile on polybutadiene

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_ 30 -

and their mixtures with the copolymers mentioned under 5), as they are known as so-called ABS polymers.

7. Halogen-containing polymers, such as polyvinyl chloride, polyvinylidene chloride, Polyvinyl fluoride, polychloroprene, chlorinated rubbers and copolymers such as vinyl chloride-vinylidene chloride, Vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

8. Polymers that differ from α, β-unsaturated acids and their Derive derivatives such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile.

9. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as Polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and their copolymers with other vinyl compounds, such as ethylene / vinyl acetate copolymers.

10. Homopolymers and copolymers of epoxies, such as polyethylene oxide, polypropylene oxide or their polyisobutylene oxide.

11. Polyacetals, such as polyoxyraethylene and those polyoxymethylenes, which contain ethylene oxide as a comonomer.

12. Polyphenylene oxides.

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13. Polyurethanes and polyureas.

14. Polycarbonates.

15. Polysulfones.

16. Polyamides and copolyamides, which are derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the derive corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12.

17. Polyesters derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding Derive lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-eyelohexane terephthalate.

18. Crosslinked polymers which are> derived from aldehydes on the one hand and phenols, ureas and melamines on the other, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

19. Alkyd resins such as glycerol-phthalic acid resins and their Mixtures with melamine-formaldehyde resins.

20. Unsaturated polyester resins that differ from copolyesters Saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking smitt a derive.

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21. Crosslinked epoxy resins derived from polyepoxides, e.g. from bis-glycidyl ethers or from cycloaliphatic ones Diepoxiden.

22. Natural polymers, such as cellulose, rubber, proteins, and their polymer-homologous chemically modified derivatives, such as Cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose.

Of these polymers, groups 1-6, 13 and 16 are to be emphasized, as in these substrates the inventive gernässen Stabilizers have a particularly striking effect.

The stabilizers of the formula I are added to the substrates in a concentration of 0.01 to 5% by weight, calculated on the basis of this stabilizing material. Preferably 0.02 to 1.0, particularly preferably 0.05 to 0.5 wt .-% of Compounds, calculated on the material to be stabilized, incorporated into it.

The stabilizers of the formula I can be added to the polymers in a simple manner by the methods customary in the art or added during their shaping processing. For example, the stabilizer with the polymer in Powder form to be mixed dry, or a solution or suspension of the stabilizer is mixed with a solution or Suspension of the polymer mixed.

809851/1103

3 y

The organic polymer stabilized in this way can also contain other stabilizers or other additives customary in plastics technology, such as those used in, for example DT-OS 2 349 962, pages 25-32, are listed.

If known stabilizers are used, synergistic Effects occur, which is especially true when using other light stabilizers or organic phosphates is often the case.

The use of antioxidants in the stabilization of polyolefins is of particular importance.

The following examples explain the invention in more detail without limiting it. In it, under parts Parts by weight and under percentages percentages by weight; the temperatures are given in degrees Celsius.

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Example 1

197.3 g of 2,6-diethyl-2,3,6-trimethylpiperidin-4-one are dissolved in 1.5 l of methanol which is saturated with ammonia. This solution is hydrogenated in a 3 l autoclave at a water pressure of 100 bar in the presence of 30 g of Raney nickel. After 24 h the solution is filtered and the solvent is evaporated. The residue is distilled in vacuo, 162 g of 2,6-dimethyl-2,3 ₃ 6-trimethyl-4'-aminopiperidine (compound no. 1) distilling over at 133-135 ° at 23 mmHg.

If a methanolic solution of methylamine is used in the above procedure instead of the NIL solution, then 2,6-diethyl-2,3,6-trimethyl-4-methylaminopiperidine is obtained (No.2) obtained with a boiling point of 132-135 ° / 21 mmHg.

The starting material is obtained in the following way: 19.6 g of 2,4,6-triethyl-2,6-d: UTiethyl-l, 2,5,6-tetrahydropyrimidine and 0.4 g of NH, Br are in 200 ml of methanol stirred while 10 ml of concentrated hydrochloric acid were added dropwise at 10 °. The reaction mixture is stirred for a further 4 hours at room temperature, then a further 20 ml of 18% HCl are added. The mixture is now heated to 30-40 ° for 7 h and finally left to stand overnight. The mixture is made alkaline by adding 40% K ^ COo solution and the methanol is distilled off in vacuo. The residue is extracted with ether, the ethereal solution is dried and concentrated

609851/1 103

steams. The residue is distilled in vacuo and yields 15.1 g of the desired product as an oil with a bp 91-93 ° / 2 mmHg.

Example 2

19.8 g of 2,6-diethyl-2,3,6-trimethyl-4-aminopiperidine are dissolved in 100 ml of toluene. At room temperature, with thorough stirring, 14 g of benzoyl chloride are added dropwise in about 45 minutes, the temperature of the reaction mixture rising to 45 °. The reaction mixture is stirred for 3 hours at 80 °, cooled to 10 Λ5 ⁰ and treated with 200 ml of 2N sodium hydroxide solution. The toluene solution is separated off, dried over sodium sulfate, evaporated to half and diluted with hexane. The product which has crystallized out is recrystallized from toluene / hexane. To yield the 2,6-diethyl-2,3, ö-trimethyl - ^ - benzamidopiperidin (No.3) of mp 160 ^0C.

If an appropriate amount of acetyl chloride, caprylic acid chloride, adipic acid dichloride is used instead of benzoyl chloride, Sebacic acid dichloride, terephthalic acid dichloride, methanesulphochloride or p-toluenesulfonic acid chloride and one proceeds in remaining as described above, the following compounds are obtained:

2,6-diethyl-2,3j6-trimethyl-4-acetamidopiperidine (No.4), Bp 105 ° / 0.005 mmHg,

2,6-diethyl-2,3,6-trimethyl-4-capryloylamidopiperidine (No.5), Bp. 115 ° / 0.005 mmHg,

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N, N ¹ -bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) adipamide, (No. 6), m.p. 191 °,

N, N ¹ -bis (2,6-diethyl-2,3 ₅ 6-trimethyl-4-piperidyl) sebacamide (No. 7), viscous, yellowish resin, N, N'-bis (2,6-diethyl- 2,3,6-trimethyl-4-piperidyl) terephthalamide (No. 8), m.p. 272 ° (dec.),

2,6-diethyl-2,3,6-trimethyl-4-methanesulfonamidopiperidine (No.9), bp. 110 ° / 0.005 mmHg,

2,6-Diethyl-2,3 _> 6-trimethyl-4-p-toluenesulfonamidopiperidine, (entry 10) m.p. 92 °.

Example 3

14.6 g of diethyl oxalate are dissolved in 100 ml of absolute Dissolved methanol. This solution takes about 15 minutes

39.6 g of 2,6-diethyl-2,3,6-trimethyl-4-aminopiperidine were added dropwise. The reaction mixture is then stirred under reflux for 12 hours, the solvent is distilled off and the residue is obtained from acetonitrile recrystallized. The N, N'-bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) oxalamide is obtained (No.11) of m.p. 142 °.

Example 4

39.7 g of 2,6-diethyl-2,3,6-trimethyl-4-methylaminopiperidine

(No. 2) are dissolved in 100 ml of toluene. Add dropwise to this solution 28.1 g of benzoyl chloride are added in about 45 minutes. The reaction is exothermic and the temperature of the reaction mixture rises to

G09851 / 1103

to approx. 54 °. The mixture is stirred for 24 hours at room temperature, diluted with 200 ml of toluene and then treated with 200 ml of 2N Caustic soda. The toluene solution is separated off, dried over sodium sulfate and evaporated. By molecular distillation of the residue at 125 ° / 0.05 mmHg, 2,6-diethyl-2,3,6-methyl-4-N-methylbenzamidopiperidine is obtained (No. 12).

Example 5

29.8 g of 2,6-diethyl-2,3,6-trimethyl-4-aminopiperidine and 9 g of urea are heated to 130 ° and kept at this temperature for 20 hours. Initially, the reaction mixture be stirred, but solidifies over time to a solid mass. The contents of the flask are recrystallized from toluene. Man receives the 2,6-diethyl-2,3,6-trimethyl ~ 4-ureidopiperidine (No. 13) from the Snip. 176 °.

Example 6

39.7 g of 2,6-diethyl-2,3,6-trimethyl-4-aminopiperidine and 9 g of ethyl carbamic acid are reacted for 8 hours at a temperature of 155 °. The reaction mixture is crystallized twice from toluene. The 1,3-bis (2,6-diethyl-2,3,6-trinethyl-4-piperidyl) urea is obtained (No.14) which sublimates at approx. 280 °.

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Example 7

29.8 g of 2,6-diethyl-2,3,6-trimethyl-4-arainopiperidine are in 100 ml of anhydrous toluene dissolved. 17.9 g of phenyl isocyanate are added dropwise to this solution in the course of about 30 minutes, with one exothermic reaction begins. The reaction mixture is then stirred at room temperature for 12 hours. That in the course of the The product which has precipitated out in the reaction is filtered off and recrystallized from toluene. 4- (3-Phenylureido) -2,6-diethyl-2,3,6-trimethylpiperidine is obtained (No. 15) of m.p. 187 °.

If, instead of phenyl isocyanate, an equivalent amount of ethyl isocyanate or hexamethylene diisocyanate is used and the rest of the procedure is as described above, 4- (3-ethylureido) -2,6-diethyl-2,3,6-trimethyl piperidine (No. 16) as a viscous, yellowish resin, or the 1,6 - ice [3- (2,6-diethyl-2,3 ₎ 6-trimethyl-4-piperidyl) ureido] -n-hexane (No. 17) of m.p. 246 °.

Example 8

7.9 g of 4- (3-phenylureido) ~ 2,6-diethyl-2.3 _s 6 ~ trimethylpiperidine are dissolved in 30 ml of methylene chloride. A solution of 12.2 g of m-chloroperbenzoic acid in 100 ml of methylene chloride is added dropwise to this solution in about 30 minutes and the mixture is then stirred for 12 hours at room temperature. The precipitated m-chlorobenzoic acid is filtered off, the methylene

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chloride solution twice with 100 ml of 2N sodium hydroxide solution, dry it over sodium sulfate and evaporated them. Crystallization of the residue from toluene gives 4- (3-phenylureido) -2,6-diethyl-2,3,6-trimethylpiperidine-1-oxyl (No.18) of m.p. 176 °.

Example 9

21.2 g of 2,6-diethyl-2,3,6-trimethyl-4-methylamino-piperidine are dissolved with 11 g of triethylamine in 100 ml of anhydrous toluene. This is done dropwise at room temperature in about 30 minutes a solution of 8 g acetyl chloride in 30 ml toluene. That The reaction mixture is stirred for a further 24 hours at room temperature, extracted twice with 50 ml of water and the toluene solution evaporated in vacuo. The residue is subjected to a short path distillation at 110 ° and 0.005 mmHg and one receives the 2,6-diethyl-2,3,6-trimethyl ~ 4- (N-methylacetamido) -piperidine (No. 19) as a yellowish, oily liquid.

Example 10

6 g of 2,6-diethyl-2,3,6-trimethyl-4-benzamidopiperidine (No. 3) are with 5.6 g of methyl iodide and 3 g of dry potash stirred in 100 ml of dimethylformamide for 48 hours at 45 °. The reaction mixture is mixed with 100 ml of water, the resulting Filtered off precipitate, washed with water and dried. Recrystallization from acetonitrile gives

609851/1 103

2621S70

the 2j6-diethyl-1,2,3,6-tetramethyl-4-benzamidopiperidine (No.20) of m.p. 183 °.

Example 11

12 g of 2,6-diethyl-2,3,6-trimethyl-4-benzamidopiperidine (No. 3) are heated to 80 ° with 100 ml of acetic anhydride for 48 hours. The excess acetic anhydride and the acetic acid formed are distilled off as completely as possible in vacuo. The residue is washed with approx. 200 ml of water and dried and recrystallized from toluene / hexane. 1-Acetyl-2,6-diethyl-2,3,6-trimethyl-4-benzamidopiper is obtained idin (No. 21) of m.p. 169 °.

Example 12

49.5 g of 2,6-diethyl-2,3,6-trimethyl-4-aminopiperidine, 71.5 g of acetic anhydride and 70.5 g of finely powdered potash are stirred in 350 ml of xylene at 130-135 ° for 24 hours. At the beginning there is a strong CO “development, which gradually ceases. The precipitated potassium acetate is filtered off and the xylene solution is evaporated in vacuo. The brownish crystal mass that remains is recrystallized twice from toluene. The l-acetyl ^ jo-diethyl ^ jSjö thus obtained
piperidine (# 22) melts at 151 °.

609851/1103

Example 13

100 parts of polypropylene powder (Moplen, Fiber grade, from Montedison) are mixed with 0.2 parts of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ~ octadecyl ester and 0.25 parts of a stabilizer from Table 1 below homogenized in the 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 raw pressed part obtained is cut out and pressed between two high-gloss hard aluminum foils with a hand-hydraulic laboratory press for 6 minutes at 260 ° and 12 tons of pressure to form a 0.5 mm thick foil, which is immediately quenched in cold water. The 0.1 mm thick test film is produced from this 0.5 mm film under exactly the same conditions. Sections of 60 44 mm each 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 carbon extinction on exposure is a measure of the photoxidative degradation of the polymer [sLBalaban et al., J.Polymer Sci. Part C, 22_ _} 1059-1071 (1969)] and experience has shown that it is associated with a decrease in the mechanical properties of the polymer.

609851/1103

_ 42 _

The exposure time until carbon extinction is achieved of 0.3, at which the sample becomes brittle, was taken as a yardstick for the effectiveness of the stabilizers and is listed in Table 1.

Table 1

stabilizer
(No. of connections
of examples 1-12) Exposure time (hours)
up to a CO extinction
from 0.30 none 956 No. 3 6350 4th ^> 7500 5 6140 6th 4390 7th 4560 10 4450 11 6210 12th 6300 14th 6830 15th 3840

609851/1103

Example 14

100 parts of polystyrene granules with 0.25 parts of a Stabilizer of the following Table 2 dry mixed, granulated in an extruder and then with a Injection molding machine molded into 2 mm thick plates. The plates obtained are 2000 and 3000 hours in the Xenotest apparatus 150 is exposed and its yellowing is determined using the yellowing factor as follows:

Yellowing factor (VF) * = Δ T (420) - Δ Τ (680)

T (560)

χ 100

where Δ T is the transmission loss that occurred during exposure at wavelengths 420 or 680 mn and T (560) is the transmission value of the unexposed sample Mean 560 nm.

Table 2

stabilizer

(Number of connections

of examples 1-12)

none No. 3

11

15th

Yellowing factor

2000h

15.7 4.4 6.6 7.7

3000h

34.8 11.1 15.5 13.3

609851/1103

Claims (6)

Claims II. Compounds of the general formula I, DP. Γϊ ■ - - < r- ■■ ■■ * R ⁷ - • N (D - ~ -ö and their isomer mixtures or their acid addition salts, in which R alkyl with 2-6 carbon atoms, R alkyl with 1-6 carbon atoms, R alkyl with 1-9 carbon atoms, phenyl, benzyl or phenethyl and R denotes alkyl with 1-6 carbon atoms, or R and R together with the carbon atom to which both are bonded form a cyclopentyl or cyclohexyl group, R is alkyl with 1-5 carbon atoms, alkenyl or alkynyl with 3-4 carbon atoms Atoms or aralkyl with 7-8 carbon atoms, R hydrogen, alkyl with 1-5 carbon atoms, alkenyl or Alkynyl with 3-4 carbon atoms or aralkyl with 7-8 carbon atoms mean, where
R and R are interchangeable, 609851/1103 R ^{7 is} hydrogen, alkyl with 1-12 carbon atoms, cycloalkyl with 5-7 carbon atoms or aralkyl with 7-8 carbon atoms, and when n is 2 and Y is a divalent hydrocarbon radical 7 13 .represents, R means hydrogen or a group -CO-R- 13th
tet, where R is hydrogen, alkyl with 1-17 carbon atoms, alkenyl with 2-5 carbon atoms, alkoxy with 1-8 carbon atoms, benzyloxy, cyclohexyloxy. Cycloalkyl with 5-7 carbon atoms, phenyl (optionally substituted by chlorine, alkyl or alkoxy groups with 1-4 carbon atoms or hydroxyl), naphthyl, styryl, aralkyl with 7-8 carbon atoms (optionally substituted in the aromatic radical) or a monovalent heterocyclic radical,
X hydrogen, an oxyl radical, Alkyl with 1-8 carbon atoms, alkenyl with 3-6 carbon atoms, alkoxyalkyl with 2-21 carbon atoms, aralkyl with 7-8 carbon atoms, its aromatic radical with chlorine, hydroxyl, alkyl with 1-4 carbon atoms or alkoxy can be substituted by 1-8 carbon atoms, furthermore X is a 2,3-epoxypropyl group, a aliphatic acyl group with 1-12 carbon atoms or one of the Groups -CH ₂ COOR ⁸ , -CH ₂ CH (R ⁹ ) -OR ¹⁰ , -COOR ¹¹ or V) -CONHR means in which R alkyl with 1-8 carbon atoms, alkenyl with 3-6 carbon atoms, phenyl, aralkyl with 7-8 carbon atoms or cyclohexyl, R hydrogen, methyl or phenyl, 609851/1103 R is hydrogen or an aliphatic, aromatic, araliphatic or alicyclic acyl group with up to 18 carbon atoms, whose aryl radical with chlorine, alkyl with 1-4 carbon atoms, Alkoxy with 1-8 carbon atoms and / or hydroxyl can be substituted, R is alkyl with 1-8 carbon atoms, phenyl, benzyl or cyclohexyl and R alkyl with 1-12 carbon atoms, aryl with 6-10 carbon atoms (the through Chlorine or alkyl with 1-4 carbon atoms can be substituted), aralkyl with 7-8 carbon atoms or cyclohexyl, η is 1, 2 or 3, and if η is 1, 13th Y is hydrogen or one of the groups -CO-R, R ¹⁵
-CO-NR ¹⁴ , -SO ₂ -R ¹⁶ , -P (R ^2O ) ₂ , -P (O) (R ^2O ) ₂ , -P (S) (R ²⁰ ) _2> -C0-R ¹⁷ -C00H or -CO-R-COOMe is where R is hydrogen, alkyl with 1-17 carbon atoms, alkenyl with 2-5 carbon atoms, alkoxy with 1-8 carbon atoms, benzyloxy, cyclohexyloxy , Cycloalkyl with 5-7 carbon atoms, phenyl (optionally substituted by chlorine, alkyl or alkoxy groups with 1-4 carbon atoms or hydroxyl), naphthyl, styryl, aralkyl with 7-8 carbon atoms (optionally substituted in the aromatic radical) or a monovalent heterocyclic radical,
R is hydrogen or alkyl with 1-4 carbon atoms, 60 9 8 51/1103 R is hydrogen or alkyl with 1-18 carbon atoms, aryl with 6-10 carbon atoms (optionally substituted with chlorine or Alkyl with 1-4 carbon atoms), aralkyl with 7-8 carbon atoms or cyclohexyl mean, or R and R together with the N atom to which they are attached, form a piperidine, pyrralidine or morpholine ring, R methyl, ethyl, phenyl, ToIy1, naphthyl or tetrahydronaphthy1, R ¹⁷ -CH ₂ CH ₂ -, -CH = CH-, - (CH ₂ ) ₃ - or o-phenylene, R alkoxy with 1-12 carbon atoms, aryloxy with 6-12 carbon atoms, alkyl with 1-12 carbon atoms, aryl with 6-14 carbon atoms, aralkyl 20th with 7-8 carbon atoms or cyclohexyl and R in an aromatic radical can also be substituted by alkyl having 1-4 carbon atoms and / or hydroxyl and Me is the equivalent of a salt-forming mono- to divalent metal cation, or Y and R together with the N atom to which they are attached form a succinimide, maleimide or phthalimide ring, and
if η is 2, Y is one of the groups -CO-, -COCO-, -CO-R-CO-, -CONH-R ¹⁹ -NHCO-, ^ PR ²⁰ , / P (O) R ²⁰ or ^ P (S) R ²⁰ , wherein 609851/1103 R alkylene with 1-10 carbon atoms, alkenylene with 2-4 carbon atoms, thiaalkenylene with one S and 2-4 carbon atoms, arylene with 6-12 carbon atoms or cyclohexylene, ίο
R alkylene with 2-10 carbon atoms, arylene with 6-13 carbon atoms or Is cyclohexylene, 7 13 and when R is hydrogen or -CO-R, Y can also be alkylene with 2-10 carbon atoms, arylene with 6-12 carbon atoms, meta- or para-xylylene or 1,4-cyclohexylene, and if η is 3, Y is a benzene-tricarbonyl radical, a 1,3,5-triazine-2,4,6-triyl radical or ^ P, ^ PO, or ^ PS. 2. Compounds according to claim 1 of the formula I, wherein R is alkyl and R is alkyl or hydrogen and the number of C atoms of R is 1 smaller than those of R and in which the number of C atoms of R is 1 smaller than that of R. 3. Compounds according to claim 2 of the formula I, in which R and R are ethyl groups, R, R and R are methyl groups and R is hydrogen. 4. Compounds according to claim 3 of the formula I, in which R is hydrogen or methyl. 609851/1103 5. Compounds according to claim 4 of the formula I, in which X is either hydrogen or an oxyl radical, a methyl group, allyl group, benzyl group, an acetyl, acrylic or crotonyl radical, a group -CH ₂ COOR (in which R ^{8 is} alkyl with 1-4 Carbon atoms) or a group -CH ₂ -CH ₂ OR (in which R is hydrogen, an aliphatic acyl group with 1-4 carbon atoms or a benzoyl group), where X is particularly preferably hydrogen or methyl, and η 1 or 2 and in the case of 13 13 n «l Y a group -CO-R (in which R is an alkyl group with 1-17 carbon atoms, a phenyl group which can be substituted by up to three identical or different lower alkyl groups and / or hydroxyl groups) or a group -SO ₂ R ¹⁶ (in which R ^{16 is} methyl, phenyl or tolyl) or a group -CONH-R (in which R is an alkyl group with 1-12 C atoms, a phenyl or a cyclohexyl group) and in the case of n = 2 Y a group -CO-, -COCO- 18 18 or -CO-R -CO- is where R is an alkylene group having 1-10 C atoms or a phenylene group, or Y is a 19 IQ Group -CONH-R -NHCO-, in which R is hexanemethylene, Is 2,4-tolylene or 4,4'-diphenylenemethane. 609851/1103 6. Compounds according to claim 5 of the formula I, wherein X is acetyl, acryloyl or crotonyl. 7. Compounds according to claim 5 of the formula I, wherein X is hydrogen or methyl. 8. Process for stabilizing organic polymers against light degradation by adding 0.01 to 5% by weight of a compound of the formula I of claim 1 to the polymer. 9. The method according to claim 8, wherein the organic polymer or a styrene homo- or copolymer is. 10. The method according to claim 8, wherein the organic polymer is a polyurethane or a polyamide. 11. Organic polymer stabilized against light degradation, characterized by a content of 0.01 to 5 wt. % _3, preferably 0.02 to 1 wt. % Of a compound of claim 1. 12. Stabilized polymer according to claim 11, characterized by the content of a compound of claim 2. 13. Stabilized polymer according to claim 11, characterized by the content of a compound of claim 3.. 609851/1103 14. Stabilized polymer according to claim 11, characterized by the content of a compound of claim 4. 15. Stabilized polymer according to claim 11, characterized by the content of a compound of claim 5. 16. Stabilized polymer according to claim 11, characterized by the content of a compound of claim 6. 17. Stabilized polymer according to claim 11, characterized by the content of a compound of claim 7. 18. Stabilized polymer according to claim 11, wherein the organic polymer is a polyolefin or a styrene homo- or Is a copolymer. 19. Stabilized polymer according to claim 11, wherein the organic polymer is a polyurethane or polyamide. 20. Stabilized polymer according to claim 11, characterized by the content of other customary additives. 21. Stabilized polymer according to claim 20, characterized by a content of one or more conventional antioxidants. 609851/1103 22. The compound 2,6-diethyl-2 ₃ 3,6-trimethyl-4-benzamidopiperidine. 23. The compound 2,6-diethyl-1,2,3,6-tetramethyl-4-benzamidopiperidine. 24. The compound N, N'-bis (2-diethyl-6 _J 2.3 _s 6-trimethyl-4-piperidyl) oxalamide. 25. The compound N ₅ N ¹ -bis (2,6-diethyl-2,3,6-trimethyl-4-piperidyl) adipamide. 26. 2 _J 6-diethyl-2 _J 3,6-trimethyl-4-p-toluolsulfonamidopiperidin Compound. 6 0 9 8 5 1/110 3