Patent GB-1481300-A (GB)
Title: Piperidine derivatives and their use as polymer stabilizers
IPC: C08L101/00
Filed: 1976-05-19
Abstract: 1481300 7,7,9,9 - Tetrasubstituted - 1,3,8 - triazaspiro[4,5]decane-2,4-dione SANKYO CO Ltd and CIBA GEIGY AG 19 May 1976 [28 May 1975] 20755/76 Heading C2C [Also in Division C3] The invention comprises compound (I) wherein R<SP>a</SP> represents a methyl group; Rb represents a C 1-6  alkyl group; R<SP>c</SP> represents an alkyl group; R<SP>d</SP> represents an alkyl, phenyl or aralkyl group; or R<SP>c</SP> and R<SP>d</SP>, together with the carbon atom to which they are attached, represent a, cycloalkyi group; one of R<SP>e</SP> and R<SP>e1</SP> represents a hydrogen atom and the other represents a C 1-6  alkyl or allyl group; n is 1 or 2; Y represents a hydrogen atom or, when neither X nor Z represents a hydrogen atom, Y represents a hydrogen atom or a methyl, ethyl, allyl or benzyl group; X represents a hydrogen atom, an oxyl radical, or a C 1-6  alkyl group, an alkenyl, benzyl or 2,3-epoxypropyl group or a group of formula -CH 2 CH 2 OR<SP>1</SP> (wherein R<SP>1</SP> represents a hydrogen atom or an aliphatic, aromatic, araliphatic or alicyclic acyl group) ; when n = 1: Z represents a hydrogen atom or an alkyl, alkenyl, aralkyl (which is unsubstituted or has one or more substituents in its aryl moiety), aryl (which is unsubstituted or has one or more chlorine and/or methyl substituents), cyclohexyl, 2,3-epoxypropyl, alkoxyalkyl, or phenoxyalkyl group, a group of formula -CH 2 .COOR<SP>2</SP> (wherein R<SP>2</SP> represents an alkyl group or a phenyl group) or a group of formula -CH 2 CHR<SP>3</SP>OR<SP>4</SP> (wherein R<SP>3</SP> represents a hydrogen atom or a methyl or phenyl group and R<SP>4</SP> represents a hydrogen atom or an aliphatic aromatic, araliphatic or alicyclic acyl group); when n=2: Z represents an alkylene group whose carbon chain is optionally interrupted by an oxygen atom or a 2-butenylene, xylylene, or arylene group (which is unsubstituted or has one or more methyl substituents), a group of formula (p) (wherein R<SP>5</SP> represents an oxygen atom or a methylene group), a group of formula -CH 2 .COOR<SP>6</SP>0CO.CH 2 - (wherein R<SP>6</SP> represents an alkylene group) or a group of formula (wherein R<SP>7</SP> represents a hydrogen atom or a methyl or phenyl group, m is 0 or 1 and R<SP>8</SP> represents an alkylene group whose carbon chain is optionally interrupted by a sulphur atom or an alkenylene, phenylene or 1,4-cyclohexylene group); and acid addition salts thereof. The compounds (I-1) may be made by reacting a compound (II) with KCN and NH 4 HC0 3  or (NH 4 ) 2 CO 3  in accordance with the reaction sequence (A); the compounds (I-2) may be formed in accordance with the reaction sequence (B), where Z<SP>1</SP> is (when n= 1) alkyl, aryl (optionally substituted by one or more of Cl or CH 3 ) or cyclohexyl, or (when n=2) alkylene or arylene (optionally substituted by one or more CH 3 ) or a group (P); compounds (I-3) are made by the reaction (C), where Hal is halogen and Z<SP>11</SP> is (when n=1) alkyl, alkenyl, aralkyl (optionally substituted in the aryl moiety), 2,3-epoxypropyl, alkoxyalkyl, phenoxyalkyl or a group or (when n= 2) alkylene (optionally interrupted by oxygen, 2-butenylene, xylylene, a group or a group -CH 2 COOR<SP>6</SP>OCOCH 2 -; compound where X is oxyl may be made by oxidizing the corresponding compounds when X is hydrogen, in known manner; compounds where X is CH 3  are made by reacting the corresponding compounds where X is hydrogen with HCHO and HCOOH; compounds where X is alkenyl or benzyl and Z is other than hydrogen are made by reacting the corresponding compound where X is hydrogen with an appropriate halide; compounds where X is hydroxyethyl and Z is other than hydrogen are made by reacting the corresponding compound where X is hydrogen with ethylene oxide and if desired the hydroxy group may be acylated; and compounds where X and Y are other than hydrogen are made by reacting a corresponding compound where Y is hydrogen with a suitable halide or sulphate. 2,6 - Diethyl -2,3,6 - trimethyl - 4 - piperidone is made by rearranging 2,4,6-triethyl-2,6-dimethyl - 1,2,5,6 - tetrahydropyrimidine with CaCl 3  in methyl ethyl ketone, or NH 4 Br in methanol. 2 - Ethyl - 2,5 - dimethyl - 1 - azaspiro[5,5]- undecan-4-one is made by reacting -2,4,6-triethyl - 2,6 - dimethyl - 1,2,5,6 - tetrahydropyrimidine with HCl, reacting the formed 5- amino - 5 - methyl - 3 - heptanone with cyclohexanone and NH 3  and reacting the resulting 2,4 - diethyl - 4 - methyl -1,5 - diazaspiro[5,5]- undec-1-ene with NH 4 Br. 3 - Allyl - 2,2,6,6 - tetramethyl - 4 - piperidone is made by reacting 2,2,6,6-tetramethyl-4- piperidone with piperidine reacting the resulting 1,2,5,6 - tetrahydro - 2,2,6,6 - tetramethyl - 4- piperidinopyridine with allyl bromide and treating the formed 5-allyl compound with acetic acid and sodium acetate. 4 - Cyano - 2,6 - diethyl - 2,3,6 - trimethyl - 4- (3 - phenylureido)piperidine is made by reacting 2,6 - diethyl - 2,3,6 - trimethyl - 4- piperidone with HCN and NH 3  and reacting the resulting 4 - amino - 4 - cyano compound with phenyl isocyanate. The compounds (I) are used for stabilizing polymers against thermal and actinic degradation. (See Division C3).