IE45327B1 - 1-oxa-4,5-diazaspiro (4,5)decanes,process for their preparation and their use as stabilizers for organic polymers - Google Patents

Abstract

of the disclosure: New 1-oxa-4,8-diazaspiro4,5!decanes are prepared by reacting a dimethyl-dialkyl-piperidone with an .alpha.-hydroxyamide in the presence of a condensation catalyst. The compounds can be used as UV stabilizers for polymers.

Description

ΓΛΤΕΝΤ APPLICATION BY (71) HOECHST AKTIENGESELLSCHAFT, A JOINT STOCK COMPANY ORGANISED AND EXISTING UNDER THE LAWS OF THE FEDERAL REPUBLIC OF GERMANY, OF 6230 FRANKFURT/MAIN 80, FEDERAL REPUBLIC OF GERMANY.

Pftce tp 327 - 2 This invention relates to l-oxo-4,8-diazaspiro[4,5] decanes, which may be used to protect organic materials from the destructive action of ultraviolet light, and to a process for their preparation.

The present invention provides compounds of the formula branched (but not cc-branched) alkyl radical having from 1 2 to 12 carbon atoms, or R and R together with the carbon atom to which they are bonded, form an optionally methyl-substituted cyclopentyl, cyclohexyl or 2,2,6,6tetramethylpiperidyl ring, of which the carbon atom 4 3 4 is the spiro atom, each of R and R is a hydrogen atom, an alkyl radical or isoalkyl radical having from 1 to carbon atoms, an aryl radical having 6 or 10 carbon atoms which may be substituted by a halogen atom or by an alkyl radical having from 1 to 4 carbon atoms, or an aralkyl radical having from 7 to 10 carbon atoms, or 3 A R and R together with the carbon atom to which they 3 2 7 - 3 are bonded, form a cycloalkyl group having from 4 to 20 carbon atoms which may be substituted by one or more alkyl groups having from 1 to 4 carbon atoms, or an optionally alkyl-substituted pyrrolidine or piperidine group the ring nitrogen atom of which cannot be in the g α-position to the spiro atom, R is a hydrogen atom, an oxygen atom, or an alkyl group having 1 to 4 carbon atoms, HX is a non-oxidizing mineral acid, an aliphatic or aromatic sulfonjc or phosphonic acid, an aliphatic mono-, di- or polycarboxylic acid or an aromatic monoor dicarboxylic acid, and m is 0 or 1 with the proviso that when N-κ does not have a basic reaction, then m is 0.

Preferred compounds of the present invention are 1 2 those in which R and R are both methyl groups and m is zero, and examples of such compounds are: 2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane, 2-ethyl-7,7,9,9-tetramethyl-l-oxa-3-oxo-4,8-diazaspiro[4,5] decane, 2-propyl-7,7,9,9-tetramethyl-l-oxa-3-oxo-4,8-diazaspiro[4.5] decane, 2-butyl-7,7,9,9,tetramethyl-1-oxa-3-OXO-4,8-diazaspiro[4.5] decane, 2-isobutyl-7,7,9,9-tetramethyl-l-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-pentyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8-diaza spiro[4.5] decane, 2-isopentyl-7,7,9,9-tetramethyl-l-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-isoheptyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8diazaspiro[4,5]decane. - 4 2 -phenyl-7,7,9,9 r-tetramethyl-l-oxa-3 -oxo-4, 8-diazaspiro [4,5] decane, 2,2,7,7,9,9-hexamethyl-l-oxa-3-oxo-4,8-diazaspiro[4,5] decane, 2,2-diethyl-7,7,9,9-tetramethyl-l-oxa-3-oxo-4,8dxazaspiro[4,5]decane, 2.2- dipropyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8diazaspiro[4,5] decane, 2.2- dibutyl-7,7,9,9-tetramethyl-l-oxa-3-oxo-4,810 diazaspiro[4,5]decane, 2.2- dipentyl-7,7,9,9-tetramethyl-l-oxa-3-oxo-4,8diazaspiro[4,5] decane, 2-ethyl-2,7,7,9,9-pentamethyl-l-oxa-3-oxo-4,8diasaspiro[4,5] decane, 2-propyl-2,7,7,9,9-pentamethyl-l-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-isopropyl-2,7,7,9,9-pentamethyl-l-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-butyl-2,7,7,9,9-pentamethyl-l-oxa-3-oxo-4,820 diazaspiro[4,5] decane, 2-isobutyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-pentyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-isopentyl-2,7,7,9,9-pentamethyl-l-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-hexyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8diazaspiro [4,5] decane, 2-heptyl-2,7,7,9,9-pentamethyl-l-oxa-3-oxO-4,830 diazaspiro[4,5]decane, 2-nonyl-2,7,7,9,9-pentamethyl-l-oxa-3-oxo-4,8diazaspiro[4,5]decane, 3 3 2 7 - 5 2-undecyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-ethyl-2-butyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-ethyl-2-pentyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8diazaspiro[4,5]decane, 2-ethyl-2-isopentyl-7,7,9,9-tetramethyl-l-oxa-3-oxo4,8-diazaspiro [4,5]decane, 2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5] 10 decane 8-oxide, 2-hexyl-2,7,7,9,9-pentamethyl-l-oxa-3-oxo-4,8diaza spiro[4,5]decane 8-oxide, 2,2-diethyl-7,7,9,9-tetramethyl, -1-oxa-3-oxo-4,8diazaspiro[4,5]decane 8-oxide, 2,2,4,4-tetramethyl-7-oxa-13-oxo-3,14-diazadispiro[5.1.4.2] tetradecane, 2.2.4.4- tetramethyl-7-oxa-14-oxo-3,15-diazadi spiro[5.1.5.2] pentadecane, 2.2.4.4- tetramethyl-7-oxa-20-oxo-3,21-diazadispiro20 [5,1,11,2]heneicosane.

The spiro compounds of the present invention in 5 which m is 0 and R is a hydrogen atom can be prepared by condensing a 2,2-dimethyl-6,6-dialkylpiperidone or a salt thereof, with an α-hydroxyamide as follows: 337 - 6 12 3 a R , R , R and R having the meanings given above.

The reaction is carried out in an organic solvent, preferably an aliphatic carboxylic acid having from 1 to 5 carbon atoms, especially acetic acid and more especially in glacial acetic acid, in the presence of a water-removing agent, for example, polyphosphoric acid or, preferably, sulfuric acid. The reaction temperature is from 20 to 180, preferably from 40 to 120 and especially from 50 to 80°C.

When using glacial acetic acid as the solvent, equimolar amounts of piperidone and a-hydroxyamide are suitably introduced into from 3 to 10 times the amount by weight of glacial acetic acid and, calculated on piperidone, twice, or when the a-hydroxyamide contains a basic centre three times, the molar amount of concentrated sulfuric acid is suitably added dropwise, whereupon the mixture is heated. The reaction temperature may be between 40 and 120°C. During the course of the reaction the sulfuric acid salts of the compounds of the invention are generally precipitated; otherwise the mixture must be concentrated. The free bases are obtained from the resulting salts by treating with ammonia or alkali metal hydroxide solution, and these bases may be converted, preferably in an organic solvent or water, into the salts of inorganic and organic acids. The compounds in which . 5 m is 0 and R is a hydrogen atom may be alkylated with alkyl halides having from 1 to 4 carbon atoms, preferably alkyl bromides or iodides . The methyl group may also be introduced by reaction with formic acid and aqueous formaldehyde solution, C0„ being & 5 split off. By treating the compounds in which R is a hydrogen atom with hydrogen peroxide, compounds in 5 which R is an oxygen atom are produced.

The 2,2-dimethyl-6, 6-dialkylpiperidor.es used as starting compounds can be produced according to known 5 methods (for example, Beilstein, Volume 21, page 249; German Offenlegungsschrift No. 1 695 753); the ahydroxyamides can be obtained as follows: OH 4^ x R CONH, The two reaction steps can be carried out according 10 to known processes. To hydrolyse the cyanohydrins, acid3, preferably sulfuric acid, to which a quantity of water equimolar to the cyanohydrin has been added, or alkaline H2°2 ^iiou^,en-Wey^' Methoden der organischem Cheraie, 4th Edition, Volume 3, pages 662-663) may be used. An especially suitable process is carried out by way of the imino-ether hydrochlorides as follows: - 8 The imino-ether hydrochloride does not, however, need to be purified before the pyrolysis.

There are limits imposed upon the synthesis of the l-oxa-4, 8-diazaspiro[4,5]decanes since it is not as easy to produce the α-hydroxyamides from long-chained carbonyl compounds as it is from short-chained carbonyl compounds.

Suitable compounds for the production of the ahydroxyamides are, for example, those that can be obtained from the cyanohydrins of the following carbonyl compounds: formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, capronaldehyde, 2-ethylbutyraldehyde, oenanthaldehyde, 2-ethylcapronaldehyde, caprylaldehyde, pelargonaldehyde, isononylaldehyde, caprinaldehyde, isodecyl15 aldehyde, laurinaldehyde, benzaldehyde, hydrocinnamaldehyde, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, hexan-2-one, methyl isobutyl ketone, heptan-2-one, heptan-3-one, heptaneone, octan-2-one, octan-3-one, nonan-2-one, nonan-5-one, undecan-2-one, undecan-6-one, trideean-2-one, methyl isopentyl ketone, ethyl isopentyl ketone, diethyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, cyclododecanone, benzophenone, acetophenone and propiophenone.

In the compounds of the present invention, each 1 2 . of R and R is a straight-chained or branched (but not in the α-position to the heterocycle) alkyl radical having from 1 to 12, preferably from 1 to 6, carbon 1 2 atoms. The compounds in which R and R are both methyl groups may be derived from the readily-available triacetone-amine and are especially preferred. 2 Alternatively, R and R together with the carbon atom to which they are bonded, form an optionally methyl¢5337 - 9 substituted cyclopentane or cyclohexane ring, or form a 2,2,6,6-tetramethylpiperidine ring of which the carbon atom 4 is the spiro atom. 2 Examples of R are methyl and of R methyl, isobutyl 1 2 and hexyl; axamples of R and R together with the carbon atom to which they are bonded are cyclopentyl, cyclohexyl and 2,2,6,6-tetramethylpiperidyl. 4 The substituents R and R stem from the a-hydroxyamide, and each is a hydrogen atom, straight-chained or branched alkyl radical having from 1 to 30 carbon atoms, an optionally halogen-substituted, preferably chlorinesubstituted, or alkyl-substituted aryl radical (in which the alkyl group has from 1 to 4 carbon atoms) having 6 or 10 carbon atoms, or an aralkyl radical having from 7 to 10 carbon atoms, of which from 1 to 4 carbon atoms belong to the aliphatic chain.

If the α-hydroxyamide is synthesized from an 4 aldehyde, R is a hydrogen atom and R is a hydrogen atom or an alkyl group having from 1 to 30, preferably from 1 to 17 and especially from 1 to 11 carbon atoms.

Alternatively, R is an aryl radical having 6 or 10 carbon atoms (phenyl or naphthyl) and optionally substituted by a halogen atom, preferably a chlorine atom, or by an alkyl radical having from 1 to 4 carbon atoms, or is an aralkyl radical having from 7 to 10 carbon atoms, from 1 to 4 carbon atoms belonging to the aliphatic chain.

When the α-hydroxyamide is obtained from a ketone, R rs an alkyl group having from 1 to 30, preferably from 1 to 10 and especially from 1 to 6 carbon atoms or an aralkyl radical having from 7 to 10 carbon atoms, the aliphatic chain of which has from 1 to 4 carbon - 10 It «5« atoms. R in this case is an alkyl radical having from 1 to 30, preferably from 1 to 17 and especially from 1 to 11 carbon atoms, or an aryl radical having 6 or 10 carbon atoms and optionally substituted by a halogen atom, preferably a chlorine atom, or by an alkyl radical having from 1 to'4 carbon atoms, or an aralkyl radical having 7 to 10 carbon atoms, the aliphatic chain of which has from 1 to 4 carbon atoms.

Examples of R are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,:undecyl, heptadeeyl, A benzyl and phenylethyl, and of R*, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-ethyl-butyl, pentyl, isopentyl, 2-ethylpentyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, 4-isopropylphenyl, 4-methylbenzyl, phenyl, phenylethyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 1naphthyl, 2-naphthyl and benzyl. 4 Also, ft and R, together with the carbon atom to which they are bonded, may form a cyeloalkyl group having from 4 to 20, preferably from 5 to 12 and especially from 5 to 7 carbon atoms. The cyeloalkyl group may be substituted by one or more alkyl groups having from 1 to 4 carbon atoms, R^ and R3 together with the carbon atom to which they are bonded, may also form an optionally alkyl-substituted pyrrolidine or piperidine ring, the nitrogen atom of which cannot be in the «-position to the spiro atom. Examples of rings formed by the incorporation of the spiro atom are cyclopentyl, 3-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, - 11 cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclopentadecyl and piperidyl.

R is preferably a hydrogen atom. It may also be an oxygen atom or an alkyl group having from 1 to 4 carbon atoms.

HX is for example a non-oxidizing mineral acid, an aliphatic sulfonic or phosphonic acid having from 1 to 30, preferably from 1 to 18 carbon atoms, an optionally alkylated aromatic sulfonic or phosphonic acid having from 6 to 25, preferably from 6 to 18 carbon atoms, and having- up to 3 alkyl groups having from 1 to 16 carbon atoms, an aliphatic, straight-chained or branched mono- or dicarboxylic acid having from 2 to 34, preferably from 2 to 18 carbon atoms, an aliphatic polycarboxylic acid having up to 4 carboxyl groups and a total of up to 16 carbon atoms, or an aromatic, optionally to c4-alkyl- or isoalkyl-substituted monoor dicarboxylic acid having from 7 to 25, preferably from 7 to 19 carbor. atoms.

More especially, HX may be phosphoric acid, phosphorous acid, sulfuric acid, phenylphosphonic acid, camphorsulfonic acid, dodecylsulfonic acid, p-toluenesulfonic acid, alkylpolyglycolethersulfonic acid, alkarylpolyglycolethersulfonic acid, acetic acid, propionic acid, octanoic acid, 2-ethylhexanoic acid, lauric acid, stearic acid, tallow fatty acid, montanic acid, succinic acid, adipic acid, azelaic acid, citric acid, tricarballyl aeid, benzoic acid, tolyl acids, ptert.-butyl-benzoic acid, phthalic acid and terephthalic acid.

In compounds in which the group 2>N-R is not Λ5327 - 12 capable of salt formation, m is 0.

The l-oxa-4,8~diazaspiro[4,5] decanes according to the invention impart to organic polymers an extraordinary stability towards decomposition by the action of heat and, especially, ultraviolet radiation. Apart from the . 5 fact that the compounds xn which R = 0 have a typical natural colour (yellow to orange-red), the colour properties of the organic polymers containing these compounds are not impaired. In this respect they are superior to the sterically hindered piperidine compounds •which are known as excellent UV stabilizers, for example triacetoneamine, some of which tend to decompose and/or discolour when heated. The compounds of the present invention are especially valuable for the light stabiliz15 ation of polyolefins, for example polyisoprene, polybutadiene, polystyrene and especially polypropylene and polyethylene of low and high density, and ethylene/ propylene, ethylene/butene, ethylene/vinyl acetate, styrene/butadiene and acrylonitrile styrene/butadiene copolymers, Other organic polymers which can be stabilized with these compounds are polyvinyl chloride, polyvinyl acetate and copolymers thereof with other olefinieally unsaturated monomers. The terra “organic polymers also includes, for example polyacetals, polyesters, polyamides, polyacrvlates, polyurethanes and epoxy resins.

The quantity of the compounds of the present invention to be added to the organic polymers can vary considerably, depending on the type, the properties and the special uses of the polymer to be stabilized.

In most cases, from 0.01 to 5 parts by weight, - 13 preferably from 0.05 to 3 parts by weight, especially from 0.1 to 1.5 parts by weight, calculated on the synthetic polymer, are used. One compound or a mixture of two or more compounds can be used.

The compounds according to the present invention can be incorporated into the organic polymers by conventional methods. Thus, the stabilizer can be mixed in the form of a powder with the polymer. Alternatively, a solution, suspension or emulsion of the stabilizer can be incorporated into the polymer directly or into a solution, suspension or emulsion of the polymer, the solvent being removed subsequently.

The stabilizers are effective on their own or in admixture with one or more conventional stabilizers, for example antioxidants based on phenols and sulfides, UV-absorbers and agents for protection against light, phosphite stabilizers, metal compounds, peroxide decomposing agents, epoxy stabilizers and polyhydric alcohols and also with antistatic agents, flameproofing agents and pigments.

Examples of suitable conventional antioxidants are those of the sterically hindered phenol type, such as 2,6-di-t.-butyl-jj-cresol, l,6-di-oc.tadeeyl-j3-cresol, 4,4' -butylider.e-bis-(2,6-di-t. -butylphenol), 4,4' -thiobis-(2-t.-butyl-5-methylphenol), phenolic triazine compounds, thiodipropionic acid esters of fatty alcohols, dioctadecyl sulfide and-disulfide.

UV absorbers and agents for protection against light include, for example, 2-(21-hydroxyphenyl)benztriazoles, such as 2-(2'-hydroxy-5'-methylphenyl)benztriazole, 2-hydroxybenzophenones such as 2-hydroxy4-octoxybenzophenone, stabilizers from the salicylate 48327 - 14 ' group, such as oetylphenyl salicylate,' nickel chelates • and oxalic acid diamides.

Trisnonylphenyl phosphite, trislauryl phosphite and esters of pentaerythritol phosphite are examples of conventional phosphite stabilizers.

Known metal compound stabilizers are, for example calcium, barium, strontium, zine, cadmium, magnesium, aluminium and lead salts of aliphatic carboxylic acids and hydroxycarboxylic acids having from about 12 to 32 carbon atoms, salts of such metals with aromatic carboxylic acids, such as benzoates or salicylates and alkylphenolates of such metals, and organotin compounds, for example dialkyltin thioglycolates and carboxylates.

Known epoxy stabilizers are, for example epoxi15 dized higher fatty acids, such as epoxidized soya bean oil, tall oil, linseed oil and epoxidized butyloleate as well as epoxides of long-chained a-olefins.

Polyhydric alcohol stabilisers are for example, pentaerythritol, trimethylol propane, sorbitol and mannitol, that is alcohols preferably having 5 to 6 carbon atoms and from 3 to 6 OH groups.

An effective stabilizer combination for poly-aolefins, for example, high, medium and low pressure polymers of to C^-a-olefins, especially polyethylene and polypropylene, and copolymers of such a-olefins comprises, per 100 parts by weight of polymer, for example from 0.01 to 5 parts by weight of one of the compounds according to the present invention, from 0.05 to 5 parts by weight of a phenolic stabilizer, option30 ally from 0.01 to 5 parts by weight of a sulfurcontaining costabilizer, and optionally from 0.01 to 3 parts by weight of a basic or neutral metal salt, for - 15 example calcium stearate or zinc stearate, and optionally from 0.1 to 5 parts by weight of a phosphite and optionally from 0.01 to 5 parts by weight of a known UV stabilizer selected from alkoxyhydroxybenzophenones, hydroxyphenylbenzotriazoles, benzylidenemalonic acid mononitrile esters and the so-called quenchers such as nickel chelates.

The following Examples illustrate the invention.

Example 1 1° 2,7,7,9,9-Pentamethyl-1-oxa-3-oxo-4,8-diazaspiro Γ 4,5] decane 31.0 g (0.2 mole) of triacetone-amine and 17.8 g (0.2 mole) of lactic acid amide are introduced into 200 g of glacial acetic acid, 43.1 g (0.44 mole) of concen15 trated H2S04 are then a^dcd dropwise while stirring, and the mixture is heated at 60°C for 40 hours. The precipitate formed on cooling is suction-filtered off (35 g = 54% of the theoretical yield of the sulfuric acid salt of the desired compound), dissolved in approximately 50 ml of water and stirred into 100 ml of concentrated The desired compound precipitates, is suction-filtered off and recrystallized from acetone, Mp. 215°C.

Examples 2 to 7 The following were prepared analogously to Example 1 from equimolar amounts of triacetone-amine and a-hydroxyamide: - IS - CI CI | σ» r4 CI t i-i 00 M* m H in CJ ci CI CI T3 Φ N •H rd «μ H H 0 0 H 0 (C 0 6 fi 0 3 «Ρ fi (ΰ ra fi »ύ ra g fij x; Λ ra 0 ih o X3 P 4J Λ k k k +J φ 0 «Ρ &j U 44 (1) g g 0) IS II τ) λ >φ ΙΛ ιη •η ο a Ε Ε * g ·η C1 ΓΠ Ϊ3 Λ ο α & 2 I Μ •γ! 0 S &’Η Ό >ι*σ Χ5 Φ II ΓΠ Ο ι ro 8 fi %5 Μ θ S Ol o φ ra S σ» Η « | φ «, I I I r* I I , *> I t Ο 0 ra fi c* H co r*-n * H GO t—, Γ> Η r—» «» Τ Ν ra «» ·. in r* fc*i * in 1 ί in C- Η ra u Cl XJ *Φ «> XJ * c* γ4 00 * I •Η φ { -P I CI 4J 1 <3. i >< Μ* Γ-» Η tf •ύ Φ 0 I Φ 0 1_i H Χ3 t—j ' >1 I ϊ“—1 βΐ ΰ r«i 0 H g X 0 >» «μ 1 Ο CJ Λ co m ft 0 k ra 0 M Χί Φ 0 Μ Ί3 1 -Ρ 0 -μ I •H •P «μ ί ¥ g κ •Η fi Η Φ k fi fp ft fi fi ω ft φ ra ρ 0» fi ί>ί g I l_l ft Φ I ra Φ Λ Φ 1 ra Φ •Η k τ ra Φ 0 xj ra 0 0 0 ra ra fi 0 ft ra ra fi »0 X» C1 ra fi ft •μ ψι κ k ra κ N ra ra 1 κ N ra 1 Φ t Ν ra & φ fi 0 •H •H Ch 0 ra □ •ri Φ G ra o CI μ ra ra u ο I Φ ί ft I * T •H φ I * 1 •H φ % I κ •Η φ ο ci α,ω ra CI σ> H Π3 ό Cl ΟΪ H Ό CI <η 0 Ό Ό 0) r4 & m rd in O Ci - 17 43327 0 σι 10 Γ* £ OJ Cl 4J *0 Φ N •d r-i r-i I—1 r4 a d 0 0 •P fi G Ό to g (0 β 0 >1 0 x; XJ P Ρ P P 4J ft ϋ ΨΙ Φ a) Φ II Ό XJ Tf. •d Q erf 1 1 g -d XT in d xj *—» »*> >4 £ Cl Cl K EC B 0 G □ ϋ Ρ -d *—* ·*-* Ό 1 1 8 s d i—1 r—1 1 CJ 1 CJ id r-4 <«. 1 >1 1 :n xi x? xj m * -P rd id •P id Ή Φ * «· Φ k ·. g CO in g CO Lfl io 1 L_j fo 1 L.iJ P 0 0 ρ Q 0 4J X 0 Ρ Φ •P X Ρ Φ Φ •d G Φ 0 •d G •P Y ft d •P 1 ft d Ό 1 CO ω o 1 xf to o G xt z-4 ri Φ rd •d Φ ΰ K 1 *& Ό K 1 TJ Π3 0 xj* d d d d d d ft X N H * X N 4J ε CJ p d -P CJ 0 d G o «. Y •h φ *. 1 •d Φ υ Cl r> Ό «Ρ Cl r> V ft v r-4 |ό | fe « $ rd H4 0 1 0 •P >1 g 0 G 0 X •d 0 d* G Ό Ό p vD Φ Φ »G Φ Ό • xj r-i Φ Φ P >1 O •P H +» P Φ XJ •d d P P ! to P •P •d »d Cl Oi •H 01 •d P •d •d ft to tp Mq r- Oi Ό •d 0 » G O Ό G Φ CJ •H G Φ G 0 G Φ J-: ΰ P d •d d Φ p XJ a. •P 0 rd •H >P P 0 Φ 0 -P Φ G T3 g » co to Λ •P to Ό •ri ei d in CO •d 01 « ϋ •d χί o d t •d «Ρ Oi 0 • 0 *3 0 0 G d Φ G P σ» •ri •d G H G •d •P P 0 0 s 0 gj σι Φ P •d «Ρ ft (0 u P •P Φ Q g d o d •P Φ 0 O o n co ca 0 ,d «—1 0 d id d \ •d Π3 d Φ P G Ό Ό C •H H rd Φ •d Φ 1 d 0 •ri d XJ •P • co d XJ •d P Ό d □ k Φ id 0 Φ Φ «Ρ 0 xf G Oi d > •d i£> 1 •d Φ H XJ H ft 01 0 g to 0» •P 0 •d id X d 0 •H •d 01 υ o | £ Φ S 01 φ • Y Φ 01 ft XJ •d P & co G 0 E4 Ό Ό ft S 1 0 O P Φ d 4J ό P φ X Φ ro P XJ • o υ *0 « •d Φ Y d 0 Φ u P 0 G td Ή -P Ό 0 01 0 1 p G Ό o Ό •P id +J •d d co 01 Φ • Φ > •d P co 0 XJ Ip Ό Φ •P Φ EC d X> 0 Φ P d Φ •P § Φ □ d 5 id § £ G to Ό •d 0 d Φ Ό xf P •d Φ P p rd 0 O G to 1 •P Ή P 0 P Cfl 0 Φ G d Φ S •P Cl X! P 0 P no •P G ffi •d XJ φ I CO •H O Φ +) G N co • no Cl XJ 0 Φ •d o Φ Φ -P G Ό id cn P •P P 01 G rd d d 0 «13 0 d Γ*· Oi P tp G 01 0 •P in φ 4J d d co r* G Ό tp 1 ID •d Φ Φ 0 Ό 0 P H Xf g Ό G G Φ □ > d G G U 0 rd Φ x: P 0 •rj d G g P •P >1 U •P > Ό w -P G 0 o Ό I G 0 G P in G CJ Λ 0 Φ •d ft rd d in O rd tn rd o CM cn cm CM I CM CM CM CO in i—ί CM I cn H CM *0 43 43 © Φ N 4J 4J •H Φ Φ r-I Φ 0 +1 r4 «Η Φ Φ 0 φ Ο 3 +J β Η »4 •0 0] £ φ >ι ih 0 >< o Λ Χί Λ k M u 43 43 •μ ft 0 Ή Φ Φ Φ 1 ιη Η Λ ιη ι*4 ι-4 □ C5 Κ a a •Η ιο r* tn Χί ϋ 9 Ο & c k -rl Ό _ >t>q js a) I. Dl M 3 Pi S3 rH sf* ui o φ 1 1 σι ι Μ σι ω 1 ·. ω ι Φ 1 - I 0 σι ι ο Or I Φ Οϊ a k • a k Φ σι X 1 Φ * 54 ·Η Γ» 54 ·Η Μ &< * 0 ω ί Φ β Ν Φ ^9 81 Γ- ? 81 » ρ-4 φ ο ο· Η π) ι η a Φ Γ*· I •Η Φ 1 1 Ν Η 1 Ν $4 * Η •ϋ Ό Η Η (Β Φ >ιΗ a φ Φ r* >t 1 Ρ—« > 5χ·Η β 4J >1·Η β £ I »c co ιη +> Λ Ό Φ α λ ό φ »0 Η 43 »» * Οί+ι 1 □ ω +ι ι α cn β ΪΗ © <4< Ο φ 00 Φ ft 0 ω φ β β β S I «—» J3 g - T3 Ή Ξ ' ‘Φ 1 Ο Φ Φ ο ο ο a a· (—“ί •α a ν γ—Ί & Λ Μ « Μ μ k ί ιη ! Μ 1 ιη 0 β ίΧ43 ρ ή •Η U Ο ΟΙ +1 ο «. Η 0 1 Φ ϊ Of 1 0 ί Β1 - Φ 54 Η Ό CM 43 cn ω CM 43 0 1_! ΟΙ +> 0 I—J <8 Φ x: EH r-i iH o r4 in r-J 4S327 - 19 Example 12 2-Propyl-7,7,9,9-tetramethyl-l-oxa-3-oxo~4,8diazaspiro[4,5] decane 77.5 g (0.5 mole) of triacetone-amine and 58.3 g (0.5 mole) of 2-hydroxyvaleramide are introduced into 500g of glacial acetic acid. 107.8 g (1.1 mole) of concentrated H^SO^ are then added dropwise while stirring and the whole is then stirred for 72 hours at 60°C. The glacis... acetic acid is then distilled off under slightly reduced pressure, the oily residue is dissolved in water and stirred into concentrated . The substance precipitated is suction-filtered off and recrystallized from ethanol. Mp. 199°C.

Example 13 2-Butyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8diazaspiro[4,5] decane The preparation of this compound is carried out analogously to Example 3 with 39.3 g (0.3 mole) of 2-hydroxycapronamids instead of 2-hydroxybutyramide, for a period of 72 hours and at a temperature of 60°C. The product is recrystallized from methanol.

Mp. 182°C. - 20 48327 Γ- ω ID Ο co ID 03 | 7 I—1 ω ID 1 Ofi Ο CO lo O 04 rH H 04 Φ Μ +J Φ Φ <3 4J N p • Φ »H a) 5 H 0 ι—1 \ 44 H rti 0 Φ Φ O (0 β $4 β S 4J p4 nJ 0 0 Ό BJ S >1 42 44 4> 0 >i 0 •B 44 Φ Φ Μ Μ M P Φ U 0 ft o m β) S Φ Φ ο w λ •Η Ο ε -η h Β $ Η Λ ω ι to ι Β S \§Ζ g ¢4 Β. r-i Η σ» Η Η Η 02 02 02 ιη m cn ο □ ο Τ •Η QJ Η r Μ Ο) 1 04 1 Η Η Φ cn 1 ♦rl ί I 0 1 1 0 >1 >1 0 . » (3 ft φ Μ σ\ Φ Μ 4J 42 φ m X ϋΓ. Φ χ •Η X «Η β 44 1 co Π3 » ο Φ * 9 ft σι 0 ft Φ Φ {—Ί ο ι Ν 0* τ ϋ] * Τ bj ft i Η 10 -Η (0 r-4 «ί ο- Η rt σ S Μ* * Γ 1 •rf 0* ( Ν . 1 Ν » μ 1 ’φ 1 Η Φ 1. η Φ Φ Η Φ Φ •Η +> 0 %—J Η >ι j β . 03 £*« •Η β *- >ί Ή β 4 Φ X 0 >ιΛ ω (ΰ 1 42 «ϋ Φ 03 XJ (ϋ 04 -Ρ 0 Μ *ϋ •Ρ Ρ κ □ r-i 4J ! □ ί 4J ι ϋ I 1 τ Ή β 3 Φ φ >1 Φ 00 Φ r—J Φ CO φ Η σι 04 ft S- . 0 €1 V δ- »0 ί—1 ti Η T? Ί-1 & § * *ϋ >j * 43 α> 4 φ W Φ ft w Μ j4 ιη Φ μ 4 m 0 •μ ι ιη 4J * X Μ S •Η 44 0 W ft β Ρ * 9 β Ρ * Φ Γ* 0 Φ 0 1 Φ ϊ <* 1 Φ X <· I Φ X χρ ι « 1 •Η Ό 03 4» η L—.| 03 ft ο«—> 03 ft 0 1—* 04 0» «Η Ό Φ ιη Φ ΓΗ r-i Η ιη ο ιη ο Η r-ί OJ 3S327 - 21 Ο •Η Μ Ψί r-j υ Ο ο υ 04 04 0 1 04 σ» σ> I a σ> σ) ΓΟ S γΗ Η 04 04 Φ Φ φ 0 4J Ρ φ β 3 β «η φ Ρ β © Φ W .Ρ φ •Ρ β 0 Λ Φ ν; β •Ρ Φ Ρ 0 Η φ Ό φ β rp \ □ • 4J • ί •Ρ γΗ φ β Ίη Ο) <Ρ rp co ϋ β β Η • β γΗ ΰ 4J 0 •Ρ Ό XI Ό 10 £ 44 ί>1 Φ Φ Ό Ρ Φ 0 0 φ XI 0 rp τ> β φ Η Ρ Ρ Ρ φ «Ρ Ρ ft τ3 β *«—' ft ft ϋ ψ» β φ •Η 5 β •Ρ Μ Φ > Λ Η +> ω φ & ο Η β α β 4J ο >ι •Ρ Τ3 Φ Φ 4J •Η Μ Ρ β U β .§ χ ο Μ ft & 4J β Ο η φ Ν •Η Η rp «ί JJ W >. Ρ ο β φ XI 4J Ό β β I ϋ β φ ιΡ ί X W Ο •Ρ ω β Ο ζη ο Η β β σ\ ο ο β Ρ ·Ρ Ό XI Φ ..

I W ΓΟ ΰ β (ύ II ϋ 04 *···> οι a ο q Ο •Η +> β Ρ β Ομ φ Μ a .» Φ XI β ε» ο •Η •Ρ ϋ <0 Φ Ρ τι ft φ β ρ •Ρ ν φ φ Φ 44 Ό Μ Φ X •Ρ M-J Ο β G •Ρ β +J Ifl β Ρ Ό -Ρ *Ρ γΡ υ ·ρ λ <ρ ο Ό β β σ> Η W Φ Η ιη σ> β 0· ιΡ χ 1 φ Η I ο ρ β β γΡ ·, ϊ Ν β «. ί>1 0· tP β υ 04 XI *· | •Ρ φ 1 •Ρ ο* rP τι τι fp φ Η >1 ι g 04 XI 00 Ίη -Ρ Λ 1 .ρ * * β •Ρ rp φ β· β· φ 6 £ ί ιη ρ Ή ft W Φ ο ftn β β ·~ · ‘ Ν β β ο Ρ Φ *ϋ β β ο ft ρ 4J X ρ W I I 0 £ ‘V β 0 •Ρ •Ρ σ· β rP 0 Φ I ft 1 * X Η υ 04 ft ω ϋΐ 04 σ» 0 ο rp ft cn «Ρ ο OJ Ο w ο Η Η οι - 22 <1U 3»·? Example 21 2,2, 7,7» 9,9-Hexamethyl-l-oxa-3-oxo-4,8-diazaspiroΓ4,5]deeane The preparation of this compound is carried out 5 analogously to Example 13, using 77.5 g (0.5 mole) of triacetone-amine and 0.5 mole of 2-hydroxyisobutyramide The sulfuric acid salt of the desired compound is precipitated during the reaction and is suctionfiltered off. Yield: 118 gs 70% of the theoretical yield. Mp. (methanol) 238°C. - 23 38327 »3 Φ C •rd fO 4J rQ CM cn rd co ω rd | m ΓΜ rd Η pH σι (X) CM CM l—l rd ffl Π3 4J Φ W N •P +> •H Φ 0 H 0 3 +) rd iH rd rd nJ ts U Φ 0 0 s 0 3 4J fi β rd id Ό ω £ 3 nJ ns >1 Of 0 >i 0 XI X! XJ X! id id M 4J +J +> P O' ft □ Φ Φ Φ Φ rd 0 » Md n x rt 0 Φ ε *rt x: (B XJ p Ό 0 C Ci P -rt ni V t-iO H x: φ I .. ΰ 3 «Η rd ΓΟ rd in aH υ Examples 22 to 30 Φ rd Of Λ ns £ a •id ifl nJ a •rd Φ Μ ό φ ο ο id Of φ Λ F* Ό β I υ !3 in O' I I 1 O' I I Ifl * nJ cn ns * Φ O' X 1 Φ Ok X I Φ * X I Φ σ' x 1 Φ - 9 nJ C * 0 nJ 0 O' Q 3 c * 9 Iti 0 O' Y N nJ I· I N nJ Y N Φ Γ* I N nJ * rd ns u * Η ns a Γ- H flf ϋ * rd ns □ O' ί Ή φ r- s -η Φ J *rd Φ Γ- 1 •rd φ * ·—i *σ Ό * rd 15 u r^. rd U Ό * rd U U r* i>i j CM >< 1 ι» ts 1 ,_, CM > 1 ,—,1 .£ 00 U? i x: co TFT CM χ: ω in 1 XJ CO in !-d p ·» rd P * «, 1 P . «» rd P «» ·. >1 Φ M· ’Φ >1 Φ M· rd Φ ’M* >1 Φ *? β i 1 t—_» Of ε ’ >1 ε ι 1--1 P g 1 Q 0 o 3 o 0 W IB Q 0 ο. 3 s 0 Φ u 8 id id P K id Φ +1 X id Φ P id Of P 0 •rd Of α o Ή r a o •rd XJ 0 0 •H I Φ 1 Of ι φ Y Of I IB T Of i Φ T Of CM P CO CO CM OfCO m (M VJ CM ftCM w ΓΟ CM ·*}* CM in CM Ο in Ο rd r-d CM σι cn cn o r-1 I 03 0 ID cn ’ 00 03 in £ «Η <31 ”d« 03 H 04 03 03 Φ Φ Φ © •P «Ρ •P •P Φ rt rt rt rt N >P -P +» P H Φ Φ φ © H ϋ ϋ 0 0 •Ρ H rt rt rt r-l rt o rt 0 rt -p H H H o • H Ό W S >1 >1 >1 rt >1 0 >i 0 £J £ί Λ Λ .rt Μ M 0 P •P •P •P •P Oi □ Ψ3 Φ © Φ © © © H cn *0 M* . 03 r-t •η a tf tf σι H E ·γΗ H tf Si tf 0 Λ in cn f? ? □ u . o a X 0 3 ϋ >ι Ό in in Λ 0 li cn tf S! tf I « cn tf 03 Cl cn B 3 tf 0 u o ϋ 1 -. 0 1 1 I : K 1 C-XO σι σ< (S M '’T ft· if N 'S i I «ΗΛΟ I >t-H 3 Η X! Ό (3 >1+1 I O o 3 m a 1 C* » I M I'd Λ I I -H 0 Η Η Ό a >1 >1 I 0 +! 43 CO O 3+1 - 0 CI § OK? X * -I +) O U' >i 0 T ·—> f UN O +1 I ί M 0 σι id -H i ' X ft Cl Ol O -OH t T -H • H ft rt I 0) >lrt 0 +1 >1 N 3 3 Λ 0 +! -H ft 0 Ό 0 “ e i 3 N 8 0 I» I M » O rt +1 *0 0 5, 0 ! Ό Λ +> 0,-, +1 I X in 0 01 O I » 1 -Φ ci σι cn —j I cl σι I » 0 ί X o'? 1 H I M •H Oi Uf rt N rt Oi 5>fH 0 ΟΛ Ό Π M 4J I 0 Oi o co o •m S - rtf V 3 C\j 4J 0 ‘-J I I σι cn i * I 0 °i a .a ^? 8* O* »-! ftJ I I M HtM Si >l-d U30 3 +1 I * 0 00 Ό 3 » M +> * 0) -P Φ 0 rt o © Ό r—, i m 0 * X «3· o I~J © W OJ ro σι O cn O in H in O OJ - 25 Example 31 2,2,4,4-Tetramethyl-7-oxa-20-oxo-3,21-diazaspiroΓ 5,1,11,2]heneico sane 45.5 g (0.3 mole) of triacetone-amine and 68.1 g (0.3 mole) of 1-hydroxyeyelododeeane carboxamide are introduced into 300 g of glacial acetic acid. 62.7 g (0.64 mole) of concentrated H2S°4 are a^^ec* while stirring.

Stirring is continued for 15 hours at 70°C and after cooling the reaction mixture, the sulfuric acid salt of the desired compound is suction-filtered off. Yield: 81 g = 59% of the theoretical yield. The salt is dissolved in ethanol/water with heating, the solution is stirred into concentrated aqueous ammonia, the precipitated amine base is suction-filtered off and recrystallized from cyclohexanone. The crystals are washed with ether. Mp. 273°C.

Example 32 2,7,7,9,9-Pentamethyi-l-oxa-3-oxo-4,8-diazaspiro(4,51 decane 8-oxlde g of the compound according to Example 1, 50 ml of methanol, 9 ml of 30% H2O2, 0.2 g of Na^O^ and 0.2 g of the ethylenediamine tetraacetie acid are heated for 48 hours at 60°C. Concentration in vacuo is carried out, not to dryness, 20 ml of water is added, suction-filtering is effected followed by recrystallization from acetone/heptane. 3.5 g of orangecolored crystals are obtained. Mp. 17O-172°C. «5337 - 26 1 N rH rH Ο cn 1* co CM H M3 © Ν •ri ι—ί X 4) pH Φ u Φ β β μ Μ . Φ «1 «ΰ 01 β Φ μ CM 0 Ν 0 Χί & co k Μ Μ μ Φ ft 0 μ Φ Χ5 O Ol O rH Φ β Φ M3 (!) U o M ft © μ 0 β M3 8 cn d β ·Η Φ •Η Ό Η •Μ Μ & Μ Ο Φ Ο +> W ϋ X ιΒ Η si Ν ι ι σι ιΒ » X ι Φ Φ Q ιβ β «. Τ Ν (3 Γ~ i-Ί IB Ο . 1 ·Η © ι ! tn tn ι Φ - t Ο Ό (BM-n > rH Φ CO I I N « >1 ι ri >1 ίΜ Η β CM X! co ιη ΧΧΌ ίθ σι M3 1 μ - +> +> I 0 β pH Φ Φ φ φ CO Φ •rl £ β 0 1—1 *0 0 Ή 3 § ·> MX Μ* r—1 0 ft Φ μ X Μ X I Μ ) ιη Η β χί fi ρ •rl ρ CM μ δ * ι-Η ο ι Φ Τ ft 1 « Φ X sf >8 υ CM ft co tn ω CM -Ρ 0 «—1 © Λ φ & £ tn tn CO 1-Ϊ ~' «> CM CM ω k μ μ β β 0 k 0 m3 •Η Φ XI φ 0 Οι > k ft 0 ιη Η φ μχ Η •Η &ι m φ φ μ β CM φ μ >1 ω •Η •Η Φ rH μ 0 £ Φ Φ ω rH μ ft XJ μ •Η Φ β 0 Φ β rl Μ ιη β Φ •Η •Η β Φ M3 X M3 Φ M3 Φ 0 •Η Οι ϋ Φ k k ω β β *0 β ft Φ •Η MX MX μ ft k > 0 Φ X φ Φ Μ •Η Φ Λ μ Φ 6 Χί β k φ μ 03 •rl Φ Φ μ rH Χί Φ Φ φ β γΗ σι μ Μ 0 ft β 01 Φ •«Η β •Η ίχ μ 0 γΗ k pH β • ϋ 0 □ CM «Η Ο 0 0 0 φ 0 Φ Φ ω ο •Η μ Η co k •Η ft Φ β φ Χί 5 M3 0 0 μ 3 ϊχ μ •«Η μ X X! μ φ μ Η Φ Ο β 0 M3 «Μ Η * 0 Η 0 M3 Οι μ Φ μ > β β Φ Φ Φ m Οι k rH β Ο «, CM μ •ρ! μ 0» Ο μ M3 β Ο 0 Μ μ •Η • 0 0 k pH M3 φ φ k •Η φ •Η 0 •rl μ Η β Φ Γ* μ β Η 0 <η Dl β •rl g Ό •β Β β ΜΗ φ MJ 03 Φ β 0 μ φ •Η 0 «ιΗ rH M3 03 01 Χί •Η β β 0 β 0 0 CM Λ Φ Φ V * μ β Η k M3 μ & φ β β Φ χ: 0 Φ ω μ Χ3 •Η M3 X Φ μ M3 Φ β M3 μ 0 •Η β Η •Η φ ϋ 0 μ 0 k σι Φ φ Φ μ μ k β ο Φ 0 Φ φ •Η 0 •rl ϋ si β M3 μ £ β CM Μ 0 Μ 0 0 •(Η >1 0 ο Μη k «*Η ι« Φ £ ο ft 0 Φ μ Ο γΗ Λ β σι Φ οι & •ιΗ ίΠ o rH in O pH CM - 27 of 205 to 207°C are precipitated.

Example 36 2-Isobutyl-2,7,7,8,9,9-hexamethyl-1-oxa-3-oxo spiroΓ4,5l decane This compound was obtained as in the above Example from 28.2 g of the product of Example 4. Mp. 138°C. Example 37 2-Hexyl-2,7,7,9,9-pentamethyl-l-oxa-3-oxo-4,8-diazaspiroΓ4,5]decane p-tert-butylbenzoate 3.10 g (0.01 mole) of the compound according to Example 24 and 1.78 g (0.01 mole) of p-tert.-butylbenzoic acid are heated for 15 minutes in 20 ml of methanol. After cooling, the precipitated white crystals are suction-filtered off. 3.7 g; Mp. 209211°C.

Example 38 2-Hexyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8diaza spiro Γ4,5]decane stearate Preparation analogous to Example 37, with 2.84 g (0.01 mole) of stearic acid. 5.0 g of white crystals are obtained. Mp. 130 to 131°C.

Example 39 2-Hexyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8diazaspiroR, 5] decane succinate Procedure as in Example 37, with 6.20 g (0.02 mole) of the compound of Example 24 and 1.18 g (0.01 mole) of succinic acid. 6.8 grams of white crystals having a melting point of 213-214°C.

Example 40 This Example shows the light-stabilizing action of the compounds according to the invention when used - 28 10 in a poly-a-olefin. 100 parts by weight of polypropylene having a melt index i,_ of approximately 6g/l0 min (determined according to ASTM D 1238-62 T) and a density of 0.96 were mixed with 0.10 parts by weight 0.20 parts by weight 0.30 parts by weight of pentaerythrityltetrakis[3-(3,5-ditert. -butyl-4hydroxyphenyi)-propionate] of calcium stearate and of one of the compounds according to the invention. on a two-roller device, at o compressed/200 C into a plate 1 mm thick. and the mixture was homogenized for 5 minutes at 200 c The plastics melt was then Test bodies were stamped out of the cooled plate in accordance with DIN 53 455. The test bodies required as comparison samples were produced analogously but with the omission of the stabilizer to be tested.

To determine the light stability the samples were subjected to radiation with alternating light in a Xenotest-150-apparatus ('Xenotest' is a . .

Trade Mark) of the firm Original Hanau Quarzlampen GmbH. The radiation intensity was modulated by 6 IR windows and 1 UV window (DIN 53 387). The exposure time was measured in hours (= service life), after which the absolute elongation at break had reduced to 10%. The elongation at break was determined on a tensile testing machine of the firm Instron (‘Instron' is a registered Trade Mark) at a draw-off speed of 5 cm/min.

The results are compiled in the following tablet «5337 - 29 Stabilizer of the invention according to Example Service life (hours) 4 <1 000 7 ooo 9 <1 000 11 <1 000 21 <1 000 26 <1 ooo without (comparison)

Claims (14)

1. CLAIMS ; 1. A compound of the general formula 1 2 in which each of R and R is a straight-chained or 5 branched (but not α-branched) alkyl radical having 1 2 from 1 to 12 carbon atoms, or R and R together with the carbon atom to which they are bonded, form an optionally methyl-substituted cyclopentyl, cyclohexyl or 2,2,6,6-tetramethylpiperidyl ring, of which the 10 carbon atom 4 is the spiro atom, 3 4 each of R and R is a hydrogen atom, an alkyl radical or isoalkyl radical having from 1 to 30 carbon atoms, an aryl radical having 6 or 10 carbon atoms which may be substituted by a halogen atom or by an alkyl 15 radical having from 1 to 4 carbon atoms, or an aralkyl 3 radical having from 7 to 10 carbon atoms, or R and Λ R together with the carbon atom to which they are bonded, form a cycloalkyl group having from 4 to 20 carbon atoms which may be substituted by one or more 20 alkyl groups having from 1 to 4 carbon atoms, or an optionally alkyl-substituted pyrrolidine or piperidine group the ring nitrogen atom of which cannot be in the a-position to the spiro atom, R^ is a hydrogen atom, an oxygen atom, or an alkyl 25 group having from 1 to 4 carbon atoms, - 31 HX is a non-oxidizing mineral acid, an aliphatic or aromatic sulfonic or phosphonic acid, an aliphatic mono-, di- or polycarboxylic acid or an aromatic mono- or dicarboxylic acid, and m is 0 or 1 with the proviso that when N-R does not have a basic reaction, then m is 0 .

2. A compound according to claim 1, in which R^ 2 5 and R are both methyl groups, R is a hydrogen atom and » is 0.

3. A compound according to claim 2, in which R is a hydrogen atom and R is a methyl, ethyl, propyl, butyl, isobutyl, pentyl, 2-ethylpropyl, 2-ethylpentyl or phenyl group.

4. A compound according to claim 2, in which R is a methyl group and R is a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, nonyl or undecyl group.

5. A compound according to claim 2, m which R is an ethyl group and R is a butyl, pentyl or isopentyl group.

6. A compound according to claim 2, in which R 3 and R are both methyl, ethyl, propyl, butyl or pentyl groups.

7. A compound according to claim 2, in which R and R together with the carbon atom to which they are bonded form a cyclopentyl, cyclohexyl or cyclododecyl ring.

8. A process for preparing a compound according to claim 1, which comprises reacting a 2,2-dimethyl6,6-dialkyIpiperidone of the formula 45337 1 2 in which R and R have the meanings specified in claim 1, or a salt thereof, with an equimolar amount of an α-hydroxyamide of the formula R 3 OH X 5 R 7 x CONH 2 3 '4 in which R and R have the meanings specified in claim 1, in an organic solvent at temperatures of front 20 to 180°C in the presence of a water-removing agent, and if desired, alkylating the product obtained with an 10 alkyl halide having from 1 to 4 carbon atoms or methylating the product obtained with a mixture of formic acid and formaldehyde, or oxidizing the product obtained with H 2 O 2 ·

9. A process according to claim 8 carried out 15 substantially as described in any one of Examples 1 to 39 herein.

10. A compound according to claim 1 whenever prepared by a process according to claim 8 or claim 9.

11. An organic polymer which contains,as stabilizer, 20 a compound according to claim 1.

12. A polymer according to claim 11 which contains the stabilizer in an amount of from 0.01 to 5% by weight, based on the polymer. ___ \ «5327 - 33

13. A polymer according to claim 11 or claim 12, which also contains one or more other stabilizers.

14. A polymer according to any one of claims 11 to 13, which is a homo- or copolymer of a halogen-free 5 α-olefin or a chlorine-containing vinyl nomo- or copolymer.