MXPA01002660A - 2,2,6,6-diethyl-dimethyl-1-alkoxy-piperidine compounds and their corresponding 1-oxides - Google Patents

2,2,6,6-diethyl-dimethyl-1-alkoxy-piperidine compounds and their corresponding 1-oxides

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Publication number
MXPA01002660A
MXPA01002660A MXPA/A/2001/002660A MXPA01002660A MXPA01002660A MX PA01002660 A MXPA01002660 A MX PA01002660A MX PA01002660 A MXPA01002660 A MX PA01002660A MX PA01002660 A MXPA01002660 A MX PA01002660A
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Mexico
Prior art keywords
ethoxy
phenyl
met
acid
ester
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MXPA/A/2001/002660A
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Spanish (es)
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Nesvadba Peter
Zink Marieodile
Kramer Andreas
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Ciba Specialtychemicals Holding Inc
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Publication of MXPA01002660A publication Critical patent/MXPA01002660A/en

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Abstract

2,2-Diethyl-6,6-dimethyl-1-(cycloalkenyl-, -phenylalkyl-, -dicycloalkylcyanomethyl-, -dimethylcyanomethyl-, -alkenyl- and substituted -alkyl- and -phenyl)-piperid-4-yl carboxylate, carbonate and carbamate ester and linear and cyclic urea compounds (IA) and corresponding 2,6-diethyl-2,3,6-trimethyl-1-substituted-piperid-4-yl compounds (IB) are new. 2,2-Diethyl-6,6-dimethyl-1-substituted-piperid-4-yl carboxylate, carbonate and carbamate ester and linear and cyclic urea compounds (IA) and corresponding 2,6-diethyl-2,3,6-trimethyl-1-substituted-piperid-4-yl compounds (IB) of the given formulae are new, except 2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)piperidin-4-yl benzoate:Y=-O-CO-R1, -C-CO-NH-R1, -N(R3)-CO-R1, N(R3)-CO-NH-R1 or -N(COR1)(COR2);and -O-X=O. The full definitions are given in the DEFINITIONS (Full Definitions)Field. Independent claims are also included for:(a) new N-oxyl compounds (II) corresponding to (IA) and (IB);(b) polymerizable compositions containing ethylenically unsaturated monomer(s) or oligomer(s) and either (I) or a combination of (II) and a free radical polymerization initiator;(c) production of a (co)oligomer, polymer or (block or random) copolymer from such compositions;(d) polymers and oligomers with bound starter group(s) -X and oxyamine group(s).

Description

COMPOUNDS OF 2, 2, 6, 6-DIETIL-DIMETHYL-L-ALCOXY-PIPERIDINES AND THEIR CORRESPONDING 1-OXIDES FIELD OF THE INVENTION The present invention relates to l-alkoxy-2,2-diethyl-6,6-dimethyl-piperidine and derivatives of l-alkoxy-2,6-diethyl-2,3,6-trimethyl-piperidine which they are substituted in the -4 position by an oxygen or nitrogen atom; a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) piperidine derivatives. Additional aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, and the use of l-alkoxy-2,2-diethyl-6,6-dimethyl-piperidine and derivatives of l-alkoxy-2,6-diethyl -2, 3, 6-trimethyl-piperidine which are substituted in the 4-position by an oxygen or nitrogen atom by controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator, as well as a process for the polymerization, are also objects of the present invention.
BACKGROUND OF THE INVENTION The compounds of the present invention provide polymeric resin products which have a polydispersity. The polymerization process proceeds with good conversion efficiency from monomer to polymer. In particular, this invention relates to stable, free-radical-mediated polymerization processes which provide homopolymers, random copolymers, block copolymers, multi-block copolymers, grafted copolymers and the like, at higher polymerization rates and higher monomer conversions. to polymer. US-A-4 581 429 to Solomon et al., Issued in April 8, 1986, describes a free radical polymerization process which controls the growth of polymer chains to produce short chains or oligomeric homopolymers and copolymers, including block copolymers and grafted copolymers. The process employs an initiator that has the formula (in part) R'R''N-0-X, where X is a free radical species capable of polymerizing more saturated monomers. The reactions typically have low conversion rates. The groups of specifically mentioned R'R''N-0'-radicals are derived from 1,1,3,3-tetraethylisoindoline, 1,1,3,3-tetrapropyl-idolone, 2, 2, 6, 6-tetramet? Lp? Pepdma, 2, 2, 5, 5-tetramet? Lp? Rrol? Dma or di-t-butylamine. However, the suggested compounds do not meet all the requirements. Particularly the polymerization of the acrylates is not proceeding fast enough and / or the conversion of monomer to polymer is not as high as desired. Recently other attempts to develop new polymerization regulators have been published. WO 98/4408 and WO 98/30601 describe heterocyclic compounds suitable for controlled polymerization processes. WO 98/13392 discloses open chain alkoxyamines which are derived from NO gas or nitroso compounds. GB 2335190 describes polymerization regulators / initiators based on 2,2,6,6-tetraalkylpiperidine, where the alkyl groups have from 1 to 6 carbon atoms and at least one group is different from methyl.
DETAILED DESCRIPTION OF THE INVENTION It has now been found that among those 2,2,6,6-tetraalkylpiperidines generically described in GB 2335190, those which are derived from l-alkoxy-2,2-diethyl- 6, 6-dimethyl-piperidine and 1-alkoxy-2,6-diethyl-2,3-b-trimethyl-piperidine and they are substituted in position 4 for an oxygen or nitrogen atom, which in themselves are further substituted. The steric hindrance introduced by the two diethyl groups leads to an optimized equilibrium in terms of the stability of the compounds, the initial activity and the control of the polymerization. The particular substitution pattern in positions 2 and 6 of the piperidm ring allows a greater conversion of monomer to polymer in short time and low polydispersities, which are generally lower than 2. Higher monomer to polymer conversions are achieved with acplates, such as ethyl or butyl acrylate. The temperature necessary to achieve a high conversion in short times can be, for example, as low as 120 ° C. The compounds exhibit a regulating / regulating activity without change even after storage at elevated temperatures, such as those used for example. in the conventional stability tests. The oxygen or nitrogen atom in the 4-position of the pipepdine ring allows a variety of substitutions. This can, for example, be used to adjust secondary polarities such as the polarity of the compound and consequently its compatibility with the mixture monomeric, oligomeric, and polymeric or also its volatility. An object of the present invention is a compound according to the formula Ia and Y 1. 0; X X (the) (lia) where Y is a radical Rx is hydrogen, -COOH, -COO (C1-C4 alkyl), -COO-phenyl, -COObenzyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 4 alkenyl, C 1 -C 8 alkyl or C 2 -C 4 alkenyl substituted by OH, -COOH, COO-alkyl of (C? -C4), C2-C? Alkyl? 8 which may be interrupted by one or more oxygen, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or unsubstituted naphthyl atoms; or cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl which are substituted by C 1 -C 4 alkyl, -COOH or -COO- (C 1 -C 4 alkyl) R 2 is hydrogen, C 1 -C 8 alkyl or Ri and R 2 together with the nitrogen atom form a 5-membered ring which may have a more saturated bond or be fused to the benzene ring; R3 is hydrogen or C? -C? 8 alkyl; and X is selected from the group consisting of - (C5-C12) -3-c-chloralkenyl, -CH2-femlo, CH3CH-phenyl, (CH3) 2C-phenyl, (C5-C6 cycloalkyl) 2CCN, (CH3) 2CCN, -CH2CH = CH2, CH3CH-CH = CH2 (C? -C4 alkyl) CR20-C (0) -phenyl, (C? -C4) alkyl -CR20-C (0) -alkoxy (C? -C), (C? -C4) alkyl -CR20-C (0) -alkyl (C -C4), (C? -C4) alkyl-CR20-C (0) -N-dialkyl of (C? -C4), (C? -C4) alkyl -CR20-C (0) -NH -alkyl of (C? -C4), alkyl of (C-C4) -CR2o ~ C (0) -NH2, where R2o is hydrogen or alkyl of (C? -C4), with the proviso that 2,6-d? Et? L-2, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -p? Pepdm-4? Is excluded. The ester of benzoic acid. The C? -C? 8 alkyl can be linear or branched. Examples are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethexyl, t-octyl. , nonyl, decyl, undecyl, dodecyl, tpdecyl, tetradecyl, hexadecyl and octadecyl. Examples of C 2 -C 8 alkyl interrupted by -0- are, for example, 3-oxapentane, 4-oxaheptane, 3,6- dioxaoctane, 4,7-dioxadecane, 9-dioxadodecane, 3,6,9-trioxaundecane and 4,7,1-trioxatridecane. The alkyl substituted by a -COOH group is for example CH2-COOH, CH2-CH2-COOH, (CH2) 3 -COOH or CH2-CHCOOH-CH2-CH3. Examples of alkoxy containing not more than 8 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy. The C2-C4 alkenyl is for example ethenyl, propenyl or butenyl; preferably ethenyl or -C (CH 3) = CH 2. The cyclohexyl substituted by COOH is for example cyclohexane-carbonic acid. The phenyl substituted by COOH is for example benzoic acid. The phenyl substituted by C-C4 alkyl is for example toluene or xylene. Preferably, X is -CH2-phenyl, CH3CH-phenyl, (3-cyclohexenyl] [CH 3) 2 C-phenyl. (Anspruch 2] More preferably X is CH3CH-phenyl, [Anspruch 3] Preferred compounds are of the formulas I or III where Y is a radical of the formula O 0 0 '"R1 R1 O N and R has the defined meanings H previously Particularly preferred are the following individual compounds. The compounds according to the formula (la). 1) 2, 6-Diethyl-2,3,6-trimethyl- 1- (1-f-enyl-ethoxy) -piperidin-4-yl ester of formic acid; (2) 2, 6-Diethyl-2, 3, 6-trimethyl-l- 1-phenyl-ethoxy) -piperidin-4-yl ester of acetic acid; (3) 2, 6-Diethyl-2,3,6- trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of propionic acid; (4) 2, 6-D? Et? L-2, 3, 6-tpmet? L- 1- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L ester of butyric acid; (5) 2, 6-D? Et? L-2,3,6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester of pentanoic acid; (6) 2, 6-D? Et? L-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? -hexanoic acid ester; (7) 2, 6-D? Et? L-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? -hetatanoic acid ester; (8) 2, 6-D? Et? L-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? l octanoic acid ester; (9) 2, 6-D? Et? L-2,3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? l ester of nonanoic acid; (10) 2, ß-D? Et? L-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? l decanoic acid ester; (11) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? pepdm-4-? undecanoic acid ester; (12) 2, 6-Diethyl-2, 3, 6- tr? methyl-1- (1-phenyl-ethoxy) -p? peridin-4-yl ester of dodecanoic acid; (13) 2, 6-Diethyl-2,3,6- trimet? l-1- (1-phenyl-ethoxy) -p? per? din-4-? ltridecanoic acid ester; 2, 6-Diethyl-2, 3, 6 Trimethyl-1- (1-phenyl-ethoxy) -piperidm-4-yl ester of tetradecanoic acid; (15) 2, 6-D? Ethyl-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -pipepdin-4-? l ester of pentade-canoic acid; (16) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester of hexadecanoic acid; (17) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? pepdm-4-? l heptadecanoic acid ester; (18) 2, 6-D? Et? L-2,3, 6- tpmet? l -1 - (1-f-enyl-ethoxy) -p? per? dm-4 -? l octadecanoic acid ester; (19) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? pepdm-4-? l methyl ester ester of carbonic acid; (20) 2, 6-D? Et? L-2,3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester ethyl ester of carbonic acid; (21)? Enc? L ester 2,6- d? et? l-2, 3, 6-tr? met? l-l- (1-phenyl-ethoxy) -p? pepdm-4-? l carbonic acid ester; (22) Ter-butyl ester 2,6- d? et? l-2, 3, 6-tr? met? l-l- (1-phenyl-ethoxy) -p? pepdm-4-? l carbonic acid ester; (23) 2, 6-D? Et? L-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? pepd? n-4-? l ester methyl ester of oxalic acid; (24) Mono- [2, 6-d? Et? L- 2, 3, 6-tpmet? L-l- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] succinic acid ester; (25) 2, 6-D? Et? L-2, 3, 6- tpmet? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester methyl ester of succinic acid; (26) mono- [2, 6-D? Et? L- 2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L] but-2-end? O? Co acid ester; (27) 2, 6-D? Et? L-2,3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l methyl ester ester of but-2-end? o? co; (28) mono- [2, 6-D? Et? L- 2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L] pentanedioic acid ester; (29) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester methyl ester of pentanedioic acid (30) mono- [2, 6-D? Et? L- 2, 3, 6-tpmet? L-l- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] ester of hexandioic acid; tpmet? l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? l ester methyl ester of hexandioic acid; (32) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester of cyclohexanecarboxylic acid; (33) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester of c? clohex-3-encarbox? l? co; (34) 2, ß-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester of benzoic acid; (35) l- [2,6-D? Et? L-2,3,6- tr? met? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-yl] 4-methyl ester of terephthalic acid; (36) l- [2,6-Diethyl-2, 3, trimethyl? l-1- (1-phenyl-ethoxy) -p? perid? n-4-yl] ester 3-methyl ester of isophthalic acid; (37) mono- [2, 6-D? Et? L-2, 3, 6 trimethyl? l-1- (1-phenyl-ethoxy) -piper? din-4-yl] ester of phthalic acid; (38) 2, 6-Diet? L-2, 3, 6- tr? methyl-1- (1-phenyl-ethoxy) -piper? dm-4-? l naphthalene-1-carboxylic acid ester (39) 2, 6-Diet? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? peridm-4-yl ester of acrylic acid; (40) 2,6-Diet? L-2,3,6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? d? n-4-? l ester of] 2-methyl-1-acrylic acid; or (42) N-O H 2, 6-D? et? l-2, 3, 6-tr? met? l- 1- (1-phenyl-ethoxy) -piper? D? N-4-yl ester of methyl-carbamic acid; (43) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? er? dm-4-? l ethyl-carbamic acid ester; (44) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l isopropylcarbamic acid ester; l (45) 2, 6-D? Et? L-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? -tert -carbamic acid ester; (46) 2, 6-D? Et? L-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? l cyclohexylcarbamic acid ester; (47) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l phenyl carbamic acid ester; (48) 2, 6-D? Et? L-2, 3, 6- tr? met? l-1- (1-phenyl-ethoxy) -p? pepdm-4-? l p-tolylcarbamic acid ester; (49) 2, 6-Diethyl-2, 3, 6 Trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of naphthalen-1-yl-carbamic acid; (50) 2, 6-Diethyl-2, 3, 6- trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of dimethylcarbamic acid; (51) 2, 6- Diet i 1-2, 3, 6-t rimet i 1-1- (1-phenyl-1-ethoxy) -piperidin--ylamine; (52) N- [2,6-Diethyl-2,3,6- trimet i 1-1- (1-phenyl-ethoxy) -piperidin-4-yl] -formamide; (53) N- [2, 6-D? Et? L-2, 3, 6 tpmet? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? l] -acetamide; (54) N- [2, 6-D? Et? L-2, 3, 6 tpmet? l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? l] -propionamide; (55) N- [2, 6-D? Et? L-2,3,6- tpmet? l-1- (1-phen l-ethoxy) -p? per? dm-4-? l] -butyramide; (56) [2, 6-D? Et? L-2, 3, 6 tpmet? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? l] -amide of pentanoic acid; (57) [2, 6-Diethyl-2, 3, 6 Trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of hexanoic acid; (58) 2, 6-Diethyl-2,3,6- trimetyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of heptanoic acid; (59) [2, 6-Diethyl-2, 3, 6 Trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of octanoic acid; (60) 2, 6-Diethyl-2,3,6- Trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of nonanoic acid; (61) [2, 6-Diethyl-2, 3, 6 trimetyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of decanoic acid; (62) [2, 6-Diethyl-2,3,6- Trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of undecanoic acid; (63) [2, 6-Diethyl-2, 3, 6 Trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of dedecanoic acid; (64) '2, 6-Diethyl-2, 3, 6- Tridecanoic acid trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide; (65) [2, 6-D? Et? L-2, 3, 6 tpmet? l-1- (1-phen? l-ethoxy?) -p? per? dm-4-? l] -amide of tetradecanoic acid; 2, 6-D? Et? L-2,3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? l] -amide of pendade-canoic acid; (67) [2, 6-D? Et? L-2, 3, 6 tr? met? l-1- (1-phenyl-ethoxy) -p? per? d? n-4-? l] -amide of hexadecic acid; (68) [2, 6-D? Et? L-2,3,6- tpmet? l-1- (1-phenyl-ethoxy) -p? per? d? n-4-? l] -amide of heptadecanoic acid; (69) [2, 6-D? Et? L-2,3,6- tr? met? l-1- (1-phenyl-ethoxy) -p? pepdm-4-? l] -amide of octadecanoic acid; (70) Methyl ester of acid [2,6-d? Et? L-2, 3,6-tr? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-yl] -carbamic; (71) Ethyl ester of acid [2,6-D? Et? L-2, 3,6-tr? Met? L-l- (1-phenyl-ethoxy) -piperidm-yl] -carbamic acid; (72) Bencil ester of acid [2,6-d? et? l-2,3,6-tpmet? l-l- (1-phen? l-ethoxy?) -p? pepdm-4-? l] -carbamic acid; The ester of [2,6-diethyl-2,3,6-tr? methyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -carbamic acid; (74) N- [2,6-Diethyl] acid 2,3,6-trimeth? L-l- (1-f-enyl-ethoxy) -p? Peridm-4-? L] -oxalamic; Methyl ester of acid N- [2,6-Diet? L-2, 3,6-tr? Methyl-l- (1-phen? L-ethoxy?) -p? Pepdm-4-yl] -oxalamic; (76) N- [2, 6-d? Ethyl- acid] 2,3,6-tr? Met? L-l- (1-phenyl? -ethoxy) -piperidin-4-yl] -schcmamic; (77) Methyl ester of acid N- [2,6-D? Et? L-2,3,6-tr? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-yl] -succinamic; (78) Acid 3- [2, 6-d? Et? L- 2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4-? Carbamo? L] acrylic; (79) Methyl ester of acid 3- [2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-licarbamoyl] -acrylic; (80) Acid 4- [2, 6-d? Et? L- 2,3,6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4-? Carbamo? L] -butyric; (81) Methyl ester of 4- [2,6-d? ethyl-2,3,6-tpmethyl-l- (1-phenyl-ethoxy) -piperidin-4-ylcarbamoyl] -butyric acid; (82) Acid 5- [2, 6-d? Et? L- 2,3,6-t rimet 11-1- (1-phenol-ethoxy?) -piperidin-4-ylcarbamoyl! -pentanoic acid; (83) Methyl ester of acid - [2,6-d? Et? L-2, 3,6-t rimethyl-1- (1-phenol-ethox?) -piper? Dm-4-ylcarbamoyl] -pentanoic acid; 6-Diet? L-2,3, 6- trimet? l-1- (1-phenyl-ethoxy) -piperidin-4-? l] -4-hydroxy-butyramide; (85) [2, 6-D? Et? L-2, 3, 6 tr-met? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? l] -amide of 6-hydrox? -hexane? co; (86) [2, 6-D? Et? L-2,3,6- Cyclohexanecarboxylic acid tpmet? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? l] -amide; (87) [2, 6-D? Et? L-2, 3, 6- t-methyl-l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? l] -amide of c-clohex-3-encarboxylic acid; (88) N- [2, 6-D? Et? L-2, 3, 6 tr? met? l-1- (1-phenyl-ethoxy) -p? pepdm-4-? l] -benzamide; (89) Methyl ester of N- [2, 6-d? et? l-2, 3, 6-tpmet? l- l- (1-f-enyl-ethoxy; p? per? dm-4-yl] -teref talamic acid; (90) Methyl ester of acid N- [2,6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-yl] -isophthalamic; (91) N- [2, 6-d? Et? L- acid] 2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4-? L] -phtalamic (92) [2, 6-D? Et? L-2,3,6- tr? met? l-1- (1-phenyl-ethoxy) -p? pepdm-4-? l] -amide of naphthalene-1-carboxylic acid; (93) N- [2, 6-D? Et? L-2,3,6- tpmet? l-1- (1-phenol-etox?) -p? per? dm-4-? l] -acplamide; (94) N- [2, 6-D? Et? L-2, 3, 6 tpmet? l-1- (1-phenol-etox?) -p? per? dm-4-? l] -2-metl-acplamide; (95) N-Butyl-N- [2, 6-D? Et? L- 2, 3, 6-tpmet? L-l- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] -acetamide Tabelle 4: Verbindungen gemass Formel (Id) (96) [2, 6-D? Et? L-2,3, 6-tpmet? L- 1- (1-f-enyl-ethoxy) -p? Pepd? N-4-? L] -urea; (97) 1- [2, 6-D? Et? L-2,3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? l] -3-met? l -urea, (98) 1- [2, 6-D? Et? L-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? l] -3-et? l-urea; (99) l- [2, 6-D? Et? L-2,3,6- tpmet? l-1- (1-f-enyl-ethoxy) -p? pepdm-4-? l] -3-? soprop? l-urea; (100) l- [2, 6-D? Et? L-2,3,6- tpmet? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? l] -3-octadec? l-urea, (101) l-C? Clohex? L-3- [2, 6- diethyl-2, 3, 6- trimethi 1-1- (1-phenyl-ethoxy) -piperidm-4-yl] -urea; l- [2,6-Diet? l-2,3,6- trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3-phenyl-urea; (103) l- [2,6-D? Ethyl-2, 3, 6 trimet-1-l- (1-phenol-ethoxy?) -piper? din-4-yl] -3-.p.-tolyl-urea; (104) l- [2, 6-Diet? L-2, 3, 6- tpmet? l-1- (1-f-enyl-ethoxy) -piperid? n-4-? l] -3-naph talen-1-yl-urea; (105) 3- [2, 6-Diethyl-2,3,6- trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -1,1-dimethyl-urea; (106) 1-Butyl-1- [2,6-Diethyl- 2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3-phenyl-urea; Tabelle 5: Verbindungen gemáss Formel (le; (107) l- [2,6-Diethyl-2,3,6- trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -pyrrolidin-2,5-dione; (108) 1- [2, 6-Diethyl-2, 3, 6 trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -pyrrole-2, 5-dione; (109) l- [2,6-Diethyl-2,3,6- trimethi1-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3,4-dimethyl-1-pyrrole-2, 5-dione; 2 ', 6'-Diethyl-2', 3 ', 6 trimethyl-1 '- (1-phenyl-ethoxy) - [1,4'] bipiperidinyl-2,6-dione; (111) 2- [2,6-Diethyl-2, 3, 6 trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -isoindole-1, 3-dione; diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -1,3-dioxo-2,3-dihydro-1H. -isoindole-5-carboxylic acid. Also particularly preferred are the following individual compounds according to the formula (Ha).
Tabelle 6: Verbindungen gemass Formel (Ha] 2, 2-Diethyl-6,6-dimethyl-1- (1- phenyl-ethoxy) -piperidin-4-yl ester of formic acid; 2,2-d? Et? L-6, 6-dimet? L-l- 1-phenyl-ethoxy) -piperidm-4-yl ester of acetic acid; 2,2-diethyl-6,6-d? Methyl-l- 1-phenyl-ethoxy) -pipepdin-4-? L propionic acid ester; 2, 2-diethyl-6,6-dimet? L- 1- (1-phenyl-ethoxy) -pipepdin-4-yl ester of butyric acid; (5) 2, 2-d? Ethyl-6,6-d? Methyl- 1- (1-phenyl-ethoxy) -piperid? N-4-yl ester of pentanoic acid; (6) 2,2-diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of hexanoic acid; (7) 2,2-diethyl-6,6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of heptanoic acid; (8) 2, 2-diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of octanoic acid; (9) 2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of nonanoic acid; (10) 2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of decanoic acid; (11) 2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl undecanoic acid ester, (12) 2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of dodecanoic acid; (13) 2, 2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of tridecanoic acid; (14) 2, 2-D? Et? L-β, 6- dimethyl? -1- (1-phenyl-ethoxy) -piper? dm-4-? l tetradecanoic acid ester; 2,2-D? Ethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -pipepdin-4-yl ester of pentadecanoic acid; (16) 2, 2-D? Et? L-6, 6- d? met? l-1- (1-phenyl-ethoxy) -p? pepdin-4-? l hexadecanoic acid ester; (17) 2,2-D? Et? L-6, 6- d? met? l-1- (1-phenyl-ethoxy) -p? pepdin-4-? l heptadecanoic acid ester; (18) 2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of octadecanoic acid; (19) 2, 2- Diet il-6, 6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl ester methyl ester of carbonic acid; 2, 2-Diethyl-6, 6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl ester ethyl ester of carbonic acid; 2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester benzyl ester of carbonic acid; (22) 2,2-Diethyl-6,6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl ester .ter. -butyl ester of carbonic acid; (23) 2, 2-Diethyl-6,6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl ester methyl ester of oxalic acid; (24) mono- [2, 2-diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] ester of succinic acid; (25) 2, 2-Diethyl-6,6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl ester methyl ester of succinic acid; (26) mono- [2,2-d? Et? L-6, 6- d? met? l-1- (1-phenyl-ethoxy) -p? per? d? n-4-? l] ester of but-2-end? o? co; (27) 2,2-D? Et? L-6, 6- d? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester methyl ester of but-2-end? o? co; (28) mono- [2,2-d? Et? L- 6,6-d? Met? L-l- (1-f-enyl-ethoxy) -p? Per? Dm-4-yl] ester of pentanedioic acid; (29) 2, 2 -D? Et? L- 6, 6- d? met? l-1- (1-phenyl-ethoxy) -p? pepd? n-4-? l ester methyl ester of pentanedioic acid; (30) mono- [2,2-d? Et? L-6,6- d? met? l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? l] ester of hexandioic acid; (31) 2,2-D? Et? L-6, 6- d? met? l-1- (1-phenyl-ethoxy) -p? pepdm-4-? ester methyl ester of hexandioic acid; (32) 2,2-D? Et? L-6,6-d? Met? L- 1- (1-phenyl-ethoxy) -p? Per? Dm-4-? Ester of cyclohexanecarboxylic acid; 1- (1-phenyl-ethoxy) -p? Pepdm-4-? L cyclohex-3-encarboxylic acid ester; (34) 1- [2,2-diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] ester 4-methyl ester of terephthalic acid; (35) l- [2,2-diethyl-6,6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] ester 3-methyl ester of isophthalic acid; (36) mono- [2,2-diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] ester of phthalic acid; (37) 2,2-Diethyl-β, 6-dimethyl- Naphthalene-1-carboxylic acid 1- (1-phenyl-ethoxy) -piperidin-4-yl ester; (38) 2,2-Diethyl-6,6-dimethyl-l- 1-phenyl-ethoxy) -piperidin-4-yl ester of acrylic acid; (39) 2, 2-Diethyl-6,6-dimethyl-l- 1-f-enyl-ethoxy) -piperidin-4-yl ester of 2-methyl acrylic acid; 2,2-Diethyl-6,6-dimethyl-l- (1-phenyl-ethoxy) -piperidin-4-yl ester of methyl-carbamic acid; (42) 2, 2- Diet il-6, 6-dimethyl- 1- (1-f-enyl-ethoxy) -piperidin-4-yl ester of ethyl-carbamic acid; (43) 2,2-D? Et? L-6, 6-d? Met? L- 1- (1-phenol-ethoxy?) -p? Per? Dm-4-? L-isopropyl carbamic acid ester; (44) 2,2-D? Et? L-6, 6- d? met? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l octadecyl carbamic acid ester; 2,2 ~ D? Et? L-6, 6-d? Met? L- 1- (1-phenyl-ethoxy) -p? Per? Dm-4-? L-cyclohexylcarbamic acid ester; (46) 2, 2-D? Et? L-6, 6-d? Met? L- 1- (1-phenyl-ethoxy) -p? Per? Dm-4-? L-cyclohexyl-carbamic acid ester; 2,2-Diethyl-6,6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl ester of p-tolylcarbamic acid; (48) 2,2-Diethyl-6, 6- Naphthalen-1-yl-carbamic acid dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester; (49) 2, 2- Diet il-6, 6-dimethyl-l- 1-phenyl-ethoxy) -piperidin-4-yl ester of dimethylcarbamic acid; (50) 2,2-Diethyl-6,6-dimethyl-1- (1-) phenyl-ethoxy) -piperidin-4-ylamine; (51) N- [2,2-D? Ethyl-6,6-dimethyl- 1- (1-f-enyl-ethoxy) -p? Peridin-4-? L] -formamide; (52) N- [2, 2-D? Et? L-6, 6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl] -acetamide; (53) N- [2,2-Diethyl-6, 6- dimethyl? -1- (1-phenyl-ethoxy) -piperidin-4-? l] -propionamide; (54) N- [2,2-Diet? L-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -butyramide; (55) '2, 2-D? Et? L-6, 6- d? met? l-1- (1-f-enyl-ethoxy) -pipepdin-4-? l] -amide of pentanoic acid; (56) [2,2-D? Et? L-6, 6- d? met? l-1- (1-f-enyl-ethoxy) -p? pepd? n-4-? l] -amide of hexanoic acid; [2, 2-d? Et? L-6, 6- d? pet? 1- (1-f-enyl-ethoxy) -p? per? dm-4-? l] -amide of heptanoic acid; (58) [2,2-D? Et? L-6, 6- d-met l-1- (1-f-enyl-ethoxy) -p? per? dm-4-? l] -amide of octanoic acid; (59) [2,2-D? Et? L-6, 6- d? met? l-1- (1-phenyl-ethoxy) -p? pepdm-4-? l] -amide of nonanoic acid; trimetyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of decanoic acid; (61) [2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of undecanoic acid; (62); 2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of dodecanoic acid; (63) [2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of tridecanoic acid; (64) [2,2-Diethyl-6, 6- Tetradecanoic acid dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide; [2,2-Diethyl-6, 6- pentadecanoic acid dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide; [2,2-Diethyl-6, 6- pentadecanoic acid dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide; (67) [2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of hexadecanoic acid; (68) [2,2-Diethyl-6, 6- dimethyl-1- (1-f-enyl-ethoxy) -piperidin-4-yl] -amide of heptadecanic acid; (69) Methyl ester of acid [2,2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -carbamic acid; Ethyl ester [2,2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-ii; carbamic (71) ° KN N-O - ethyl ester of [2, 2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -carbamic acid; Ter. -butyl ester of [2,2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -carbamic acid; N- [2, 2-diethyl-6, 6-acid] dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -oxalamic; Methyl ester of acid N- [2,2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -oxalamic acid; (75) N- [2,2-diethyl] acid 6, 6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -succinnamic, Methyl ester of acid N- [2,2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -succinnamic acid; (77) Acid 3- [2,2-d? Et? L- 6,6-d? Met? L-l- (1-f-enyl-ethoxy) -p? Pepdm-4-? Lcarbamo? L] acrylic; (78) Methyl ester of acid 3- [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-ylcarbamoyl] -acrylic (79) Acid 4- [2,2-d? Et? L- 6,6-d? Met? L-l- (1-f-enyl-ethoxy) -p? Pepdm-4-? Lcarbamo? L] butyric; (80) Methyl ester 4- [2,2-d? et? l-6,6-d? met? l-l- (1-f-enyl-ethoxy) -p? pepdm-4-? lcarbamo? l] -butyric acid; (81) 5- [2, 2-diethyl] acid 6, 6-dimethyl-1- (1-f-enyl-ethoxy) -piperidin-4-ylcarbamoyl] -pentanoic acid; (82) Methyl ester of acid - [2, 2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-ylcarbamoyl] -pentanoic acid; (83) N- [2,2-Diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -4-hydroxy-butyramide; (84) [2,2-Diethyl-6,6- 6-hydroxyhexanoic acid dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide; (85) [2,2-Diethyl-6, 6- Cyclohexanecarboxylic acid dimethyl-1- (1-f-enyl-ethoxy) -piperidin-4-yl] -amide; (86) [2,2-Diethyl-6, 6- Cyclohex-3-enecarboxylic acid dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide; (87) N- [2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -benzamide; N- [2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -terephthalamic acid methyl ester; (89) Methyl ester of acid N- [2,2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -isophthalamic acid; N- [2,2-diethyl-6,6- acid dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -phthalamic acid; (91) [2, 2-Diethyl-6,6-dimethyl- Naphthalene-1-carboxylic acid 1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide; (92) N- [2, 2-Diethyl-6,6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl] -acrylamide; (93) N- [2,2-Diethyl-6,6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl] -2-methyl-acrylamide; (94) N-Butyl-.N.- [2,2-diethyl- 6,6-Dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -acetamide [2,2-Diethyl-6,6-dimethyl-l- 1-f-enyl-ethoxy) -piperidin-4-yl] -urea; (96) 1- [2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3-methyl-urea; 1-Et i 1-3- [2-et il-2, 6, 6- trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -urea; (98) l- [2,2-Diethyl-6,6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3-isopropyl-urea; (99) l- [2,2-Diethyl-6,6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3-octadecyl-urea, (100) l-Cyclohexyl-3- [2,2- diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -urea; (101) l- [2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3-phenyl-urea; (102) l- [2,2-Diethyl-6,6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3-.p.-tolyl-urea; (103) l- [2,2-Diethyl-6,6- dimethyl-1- (1-f-enyl-ethoxy) -piperidin-4-yl] -3-naph-talen-1-yl-urea; 3- [2,2-Diethyl-6, 6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -1, 1-dimethyl-urea, (105) 1 -But i 1-1- [2,2-diethyl- 6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3-phenyl-urea, (106) l- [2,2-Diethyl-6,6-dimethyl- 1- (1-phenyl-ethoxy) -piperidin-4-yl] -pyrrole idin-2, 5-dione; dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -pyrrole-2, 5-dione, (108) l- [2,2-Diethyl-6,6- dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -3, -dimethyl-pyrrole-2, 5-dione; dimethyl-1 '- (1-phenyl-ethoxy) - [1,4'] bipiperidinyl-2, β-dione; dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -isoindole-1,3-dione; (111) Acid 2- [2,2- Diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -1,3-dioxo-2,3-dihydro-1 H -isoindole-5-carboxylic acid.
The compounds according to the formulas la and Ha can be prepared according to standard methods. The 4-OH intermediates are prepared as described in GB 2335190. If Y is -C (0) -R or-C (0) NH-R? the intermediaries of 4-OH are reacted with the desired carbonic acid derivatives or isocyanates according to the general scheme set out below: The most preferred are the following compounds: (1) 2, 6-d? Et? L-2, 3, 6 -tpmet? ll- (1-phenyl-ethoxy) -p? pepdm-4-l ester of formic acid; (2) 2, ß-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L acetic acid ester; (3) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L propionic acid ester; (4) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? -butyric acid ester; (5) 2, ß-d? Et? L-2, 3, 6-tnmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L pentanoic acid ester; (6) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L ester of exanoic acid; (7) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? -hetatanoic acid ester; (8) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L octanoic acid ester; (9) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? N nonanoic acid ester; (10) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-decanoic acid ester; (11) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4- l undecanoic acid ester; (12) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4- ll dodecanoic acid ester; (13) 2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4-tldecanoic acid ester; (14) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4- l tetradecanoic acid ester; (15) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4-pentadecanoic acid ester; (16) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-hexadecanoic acid ester; (17) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4- ll heptadecanoic acid ester; (18) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl octadecanoic acid ester; (19) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? -foric acid ester; (20) 2, 2-diet11-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L acetic acid ester; (21) 2, 2-diethyl-6,6-d? Met? L-l- (1-fem-ethoxy) -p? Per? Dm-4-? L propionic acid ester; (22) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L-butyric acid ester; (23) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? S pentanoic acid ester; (24) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L hexanoic acid ester; (25) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L heptanoic acid ester; (26) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L octanoic acid ester; (27) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L nonanoic acid ester; (28) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? Decanoic acid ester; (29) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L undecanoic acid ester; (30) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L dodecanoic acid ester; (31) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Per? Dm-4-? Ltridecanoic acid ester; (32) 2, 2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of tetradecanoic acid; (33) 2,2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of pentadecanoic acid; (34) 2, 2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of hexadecanoic acid; (35) 2, 2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of heptadecanoic acid; (36) 2,2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of octadecanoic acid; The 4-amino, 1-oxyl intermediates are prepared, for example, by reductive amination of the corresponding 4-oxo compound, which itself is prepared as described in GB 2335190.
If Y is -NR3-C (0) -R? or -NR3-C (O) -NHRi the 4-amino or 4-alkylamino compounds are reacted with carbonic acid derivatives (chloride, anhydride or acid ester) carbon) or isocyanates. It is also possible to start from the corresponding piperidine compounds and oxidize the intermediates to the corresponding N-oxides. This is described, for example, in US 4 191 683. The nitroxides are then converted to the corresponding alkoxyamides as described in GB 2335190. This is outlined schematically below: if Y is R? -C (O) -N-C (O) -R2 the preparation is made according to US 4 191 683 starting from the corresponding 4- (alkyl) ammopiperidine compounds.
A further object of the invention is a polimepable composition, comprising a) at least one ethylenically unsaturated monomer or oligomer, and b) a compound of the formula Ia or Ha. Y N 'N' X X (the) (IIa) where Y is a radical R x is hydrogen, -COOH, -COO (C 1 -C 4 alkyl), -COO-phenyl, -COO benzyl, C 1 -C 8 alkoxy, Cl-C 18 alkyl, C 2 -C alkenyl, C 1 alkyl- C? 8 or C2-C4 alkenyl substituted by OH, -COOH, -COO (C? -C4) alkyl, C2-C18 alkyl which may be interrupted by one or more oxygen atoms, cyclopentyl, cyclohexyl, cyclohexenyl , phenyl or unsubstituted naphthyl; or cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl which are substituted by C? -C alkyl, -COOH or -COO- (C? -C4 alkyl) R2 is hydrogen, C? -C18 alkyl or Rx and R2 together with the nitrogen atom they form a 5-membered ring, the which may have an unsaturated bond or be fused to a benzene ring; R3 is hydrogen or C? -C? 8 alkyl; and X is selected from the group consisting of - (Cc-Cx?) - 3-cycloalkenyl, -CH2-phenyl, CH3CH-phenyl, (CH3) 2C-phenyl, (C5-C6 cycloalkyl) 2CCN, (CH3) CCN, -CH2CH = CH2, CH3CH-CH = CH2 (C? -C4 alkyl) CR20-C (0) -phenyl, alkyl (of C? -C4) -CR20-C (0) -alkoxy (of C? -C4) ), alkyl (of C? -C4) -CR20-C (0) -alkyl (of Cx-C4), alkyl (of C? -C4) -CR20-C (0) -N-dialkyl (of C? - C4), alkyl (of C-C4) -CR20-C (O) -NH alkyl (of C? -C4), alkyl (of C-C4) -CR20-C (0) -NH2, where R2o is hydrogen or alkyl (of C? -C4); with the proviso that 2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of benzoic acid is excluded.
Definitions for substituents and preferred formulas have already been given. They also apply to compositions that include preferences. Typically the ethylenically unsaturated monomer or oligomer is selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, acid hydridides (alkyl) ) Acrylics, salts of acid (alkyl) acrylic, esters (alkyl) acrylics, (meth) acrylonitriles, (alkyl) acrylamides, vinyl halides or vinylidene halides. The preferred ethylenically unsaturated monomers are ethylene, propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene, C5-C18 alkene, styrene, α-methyl styrene, p-methyl styrene or a compound of formula CH2 = C (Ra) - (C = Z) -Rb, where Ra is hydrogen or C? -C4 alkyl, Rb is NH, 0 ~ (Me +), glycidyl, unsubstituted C? -C? Alkoxy, C2-C? Alkoxy or interrupted by at least one N and / or atom, or C? -C18 alkoxy, substituted with hydroxy, C? alkylamino? Unsubstituted Cs, di (C? -C? 8 alkyl) amino, alkylamino of Ci-Cs substituted by hydroxy or di (C? -C18 alkyl) amino substituted by hydroxy, -0-CH -CH-N (CH3) 2 or -0-CH2-CH2-N + H (CH3) 2 An " An "is an anion of a monovalent organic or inorganic acid; I am a monovalent metal atom or the ammonium ion. Z is oxygen or sulfur. (Anspruch 10) Examples of Ra as U-Cio alkoxy; interrupted by at least one O atom are of the formula where Rc is C? -C25 alkyl, phenyl or phenyl substituted by C 1 -C 8 alkyl, R d is hydrogen or methyl and v is a number from 1 to 50. These monomers are derived, for example, from nonionic surfactants by acrylation of the corresponding alkoxylated alcohols or phenols. The repeating units can be derived from ethylene oxide, propylene oxide or mixtures of both. Additional examples of suitable acrylate monomers and methacrylates are given below. where An "and Ra have the meanings defined above and Re is methyl or benzyl, An" is preferably Cl ", Br" or "03S-CH3, The additional acrylate monomers are Examples for suitable monomers other than acrylates are • NV Preferably Ra is hydrogen or methyl, Rb is NH2, glycidyl, C? -C4 alkoxy, unsubstituted or substituted by hydroxy, unsubstituted C? -C4 alkylamino, di (C? -C4 alkyl) amino, C? -C4 alkylamino substituted by hydroxy or di ( C 1 -C 4 alkyl) amino substituted by hydroxy; and Z is oxygen. Particularly preferred ethylenically unsaturated monomers are styrene, methacrylate, ethylacrylate, butylacrylate, isobutylacrylate, ter. butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethylacrylate, glycidyl acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (met) acrylates, acrylonitrile, acrylamide, methacrylamide or dimethylaminopropyl methacrylamide. Preferably the initiator compound is present in an amount of 0.01 mol% to 30 mol%, more preferably in an amount of 0.1 mol% to 20 mol% and more preferably in an amount of 0.1 mol% to 10 mol % based on monomer or monomer mixture. When mixtures of monomers are used, mol% is calculated on the average molecular weight of the mixture.
Another object of the present invention is a process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically unsaturated monomer or oligomer, which comprises (co) polymerizing the monomer / oligomers in the presence of an initiator compound of formula la or Ha under reaction conditions capable of effecting the cleavage of the 0-C bond to form two free radicals, the radical "X being capable of initiating polymerization. Preferably, the cleavage of the O-C bond is effected by ultrasonic treatment, heating or exposure to electromagnetic radiation, which fluctuates from? to the microwaves. More preferably, the cleavage of the O-C bond is carried out by heating and takes place at a temperature between 50 ° C and 160 ° C. The process can be carried out in the presence of an organic solvent or in the presence of water or in mixtures of organic solvents and water. Additional cosolvents or surfactants may be present, such as glycols or ammonium salts of fatty acids. Other suitable co-solvents are described hereinafter.
Preferred processes use as few solvents as possible. The reaction mixture is preferred to use more than 30% by weight of monomer and initiator, particularly preferably more than 50% and more preferably more than 80%. If organic solvents are used, suitable solvents or solvent mixtures are typically pure alkanes (hexane, heptane, octane, isooctane), hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethylene glycol) , ethylene glycol monomethyl ether), esters (ethyl acetate, propyl, butyl acetate or hexyl) and ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether), or mixtures thereof. The aqueous polymerization reactions may be supplemented with a water-miscible or hydrophilic cosolvent to help ensure that the reaction mixture remains a single homogeneous phase through monomer conversion. Any water-soluble or water-miscible cosolvent may be used, as long as the aqueous solvent medium is effective to provide a solvent system that prevents the precipitation or phase separation of the reactants or polymer products until after all the reactions of polymerization have been completed. The exemplary cosolvents, useful in present invention can be selected from the group consisting of aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkyl pyrrolidones, N-alkyl pyrrolidones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids and salts thereof, esters, organosulfides , sulfoxides, sulfones, alcohol derivatives, hydroxy ether derivatives such as butyl carbitol or cellosolve, amino alcohols, ketones, and the like, as well as derivatives thereof and mixtures thereof. Specific examples include methanol, ethanol, propanol, dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dipropylene glycol, tetrahydrofuran, and other water-soluble or water miscible materials, and mixtures thereof. When mixtures of water-soluble and water-miscible organic liquids are selected as the aqueous reaction media, the weight ratio of water to cosolvent is typically in the range of about 100: 0 to about 10:90. The process is particularly useful for the preparation of block copolymers. Block copolymers are, for example, copolymers of polystyrene and polyacrylate blocks (for example, poly (styrene-co-acrylate) or poly (styrene-co-acrylate-co-styrene) .They are useful as adhesives or as compatibilizers for polymeric mixtures or as polymer reinforcing agents. Two-block copolymers of poly (methyl methacrylate-co-acrylate) or the three-block copolymers of poly (methylacrylate-co-acrylate-co-meta-plate)) are useful as dispersing agents for coating systems, as coating additives (for example rheological agents, compatibilizers, reactive diluents) or as a ream component in coatings (for example, highly solid paints). The block copolymers of styrene, (meth) acrylics and / or acrylonitrils are useful for plastics, elastomers and adhesives. In addition, the block copolymers of this invention, wherein the blocks are alternated between polar monomers and non-polar monomers, are useful in many applications as amphiphilic surfactants or dispersants to prepare highly uniform polymer blends. The (co) polymers of the present invention can have a number average molecular weight of from 1,000 to 400,000 g / mol, preferably from 2,000 to 250,000 g / mol and, more preferably, from 2,000 to 200 mol. 000 g / mol. When they are produced in bulk, the numerical average molecular weight can be up to 500,000 (with the same minimum weights mentioned above). The numerical average molecular weight can be determined by exclusion chromatography by size (SEC), gel permeation chromatography (GPC), laser-assisted desorption / ionization mass spectrometry (MALDI-MS) or, if the primer contains a group which can be easily distinguished from the monomers, by NMR spectroscopy (Nuclear Magnetic Resonance) or other conventional methods. The polymers or copolymers of the present invention preferably have a polydispersity of from 1.0 to 2, more preferably from 1.1 to 1.9 and more preferably from 1.1 to 1.8. Thus, the present invention also encompasses the synthesis of block, multi-block, stellate, gradient, random, hyperbranched and novel dendritic copolymers, as well as grafts or copolymers. The polymers prepared by the present invention are useful for the following applications: adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubricants, rheology modifiers, thickeners, crosslinkers, paper treatment, water treatment, electronic materials, paints, coatings, photography, materials for inks, materials for forming images, superabsorbents, cosmetics, products for the hair, preservatives, biocide materials or modifiers of asphalt, leather, textiles, ceramics and wood. Because the polymerization herein is a "living" polymerization, it can be initiated and stopped practically at will. In addition, the polymeric product retains the functional alkoxyamine group which allows the continuation of the polymerization in living matter. Thus, in one of the embodiments of this invention, once the first monomer is consumed in the initial polymerization step a second monomer can be added to form a second block on the growing polymer chain in a second step of polymerization. Therefore, it is possible to carry out further polymerizations with the same or different monomers to prepare multi-block copolymers. In addition, since this is a radical polymerization, blocks can be prepared in essentially any order. One is not necessarily restricted to the preparation of block copolymers where the sequential polymerization steps must flow from the less stabilized intermediate polymer to the more stabilized intermediate polymer, such as in the case of ionic polymerization. In this way, it is possible to prepare a multi-block copolymer in which a block of polyacrylonitrile or poly (meth) acrylate, then a block of styrene or butadiene is added to this, and so on. In addition, a linking group is not required to join the different blocks of the present block copolymer. Successive monomers can simply be added to form successive blocks. A plurality of specifically designed polymers and copolymers are accessible by the present invention, such as stellated and grafted (co) polymers as described, inter alia, by C. J. Hawker in Angew. Chemie, 1995, 107, pages 1623-1627, dendrimers as described by K. Matyaszewski et al. in Macromolecules 1996, Vol 29, No. 12, pages 4167-4171, grafted (co) polymers as described by C. J. Hawker et al. in Macromol. Chem. Phys. 198, 155-166 (1997), random copolymers as described by CJ Hawker in Macromolecules 1996, 29, 2686-2688, or two-block or three-block copolymers as described by NA Listigovers in Macromolecules 1996, 29, 8992-8993. A further aspect of the present invention is a polymer or oligomer, which has at least one initiator group -X and at least one oxamino group of the formula Ia or Ha.
The compounds of formula la and Ha can be prepared from the corresponding nitroxides, which are intermediates of the compounds of formula la and Ha. Therefore, another object of the present invention are nitroxides of formula Illa and IVa.
And Y .1 N N i O. O- (Illa) ('Va) where Y is a radical 9 O 0 R3: 0 R1 ^ 2 R3 O '' R, or N '"1" N R * ~. N! N R 'N R1: N. R "N N R, and i 1? 0O NN O H H ii HH ¡! Rx is hydrogen, -COOH, -COO (C? -C4 alkyl), -COO-phenyl, -COObenzyl, C? -C8 alkoxy, C? -C18 alkyl, C2-C4 alkenyl, C? -C? 8 alkyl or C2-C4 alkenyl substituted by, -COOH, -COO -alkyl of (C? -C4), C2-C? alkyl, which may be interrupted by one or more oxygen atoms, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or unsubstituted naphthyl; or cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl which are substituted by C? -C alkyl, -COOH or -COO- (C-C4 alkyl) R2 is hydrogen, C?-C18 alkyl or Rx and R2 together with the nitrogen atom form a 5-membered ring which may have an unsaturated bond or be fused to a benzene ring; R3 is hydrogen or C? -C? 8 alkyl; with the proviso that 2,6-diethyl-2,3,6-trimethyl-4-lauroyloxypi-eridin-1-oxyl, 2,6-diethyl-2,3,6-trimethyl-4-stearoyloxypiperidin-1- oxyl, 2,2-dimethyl-6,6-diethyl-4-lauroyloxypiperidin-1-oxyl and 2,2-dimethyl-β, 6-diethyl-4-stearoyloxypiperidine-1-oxyl are excluded. The definitions for substituents, as well as their preferences have already given. They also apply to the compounds of formula Illa and IVa. Particular preference is given to the individual compounds according to the formulas a and Ha, given above, for which the corresponding N-oxides are precursors, which therefore are also of particular interest. The compounds of formula Ha and IVa are also particularly useful for controlled polymerization reactions in combination with a source of free radicals. Also object of the present invention is a polymerizable composition, comprising a) at least one ethylenically ethylenically saturated monomer or oligomer, and b) a compound of formula Illa or IVa and c) a source of free radicals capable of initiating the polymerization of the ethylenically unsaturated monomers. The production of C-centered radicals is described, inter alia, in Houben Weyl, Methoden der Organischen Chemie, Vol. E 19a, pages 60-147. These methods can be applied by analogy in general. The source of radicals can be a bis-azo compound, a peroxide or a hydroperoxide. Preferably, the source of radicals is 2,2'-azobisisobutyronityl, 2,2'-azobis (2-methyl-butyronitop), 2,2'-azobis (2,4-d? Met? Lvalerron? Tr? lo), 2,2'-azobis (4-methox? -2, 4-d? met? lvaleron? tlo), 1, 1 '-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis dihydrate (isobutyramide) ), 2-phenol-2, 4-dimethyl-4-methoxivaleronitin, d -methyl-2, 2'-azobisisobutyrate, 2- (carbamoylazo) isobutyronitop, 2,2'-azobis (2, 4, 4) -tpmet? l-pentane), 2, 2'-azobis (2-met? lpropane), 2, 2'-azobis (N, '-dimethylene-isobutyramide), free base or hydrochloride, 2,2'-azobis (2- ammopropane), free base or hydrochloride, 2,2'-azobis. { 2-met? L-N- [1, 1-b? S (hydroxymethyl) ethyl] propionamide} or 2,2'-azob? S. { 2-methyl-N- [1,1-b? S (hydroxymethyl) -2-hydrox? Et? L] propionamide. The preferred peroxides and hydroperoxides are acetyl cyclohexane sulfonyl peroxide, dnsopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, bis (2,4-d? Chlorobenzo? l) peroxide, dusononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis (2-meth? lbenzo? l) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, per 2-et? t-butyl lhexanoate, bis- (4-chlorobenzoyl) peroperoxide, t-butyl perisobutyrate, t-butyl permaleinate, 1,1-b? s (t-butylperoxy) 3, 5, 5-tr? methac? clohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl pepsononatoate, 2,5-d-benzoate 2,5-d? methexanoxane, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-b? s (t-butylperoxy) butane, 2,2 bis (t-butylperoxy) propane, dicumyl peroxide, 2, 5 -d? met? lhexan-2, 5-d? -t-bu tolophore, 3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, a, a'-bis (t-butylperoxy isopropyl) benzene, 3,5-b? s (t-butylperoxy) 3 , 5-d? Met? 1, 2-d? Oxolane, di-t-butyl peroxide, 2,5-d? Met? Lhexm-2, 5-d? -t-but? Peroxid, 3 , 3,6,6,9,9-hexamethyl 1,2, 5-tetraoxa cyclononane, p-hydroperoxide menthane, pineane hydroperoxide, diisopropylbenzene mono-a-hydroperoxide, eumeno hydroperoxide or t-butyl hydroperoxide. These compounds are commercially available. If more than one source of radicals is used, a mixture of substitution patterns can be obtained. The source of radicals is preferably present in an amount of 0.01 mol% to 30 mol%, more preferably in an amount of 0.1 mol% to 20 mol% and more preferably in an amount of 0.5 mol% to 10 mol% based on the monomer or monomer mixture. The molar ratio of the radical source to the compound of formula II can be from 1:10 to 10: 1, preferably from 1: 5 to 5: 1 and more preferably 1: 2 to 2: 1. Still another object of the present invention is a process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically unsaturated monomer / oligomer, which comprises subjecting the composition prior to heat or actinic radiation. The additional objects of the invention are the use of a compound of formula la or Ha AND AND I N N for the polymerization of ° X? (the) (Ha) ethylenically unsaturated monomers and the use of a compound ? Y of formula Illa or IVa N N i together with O- ° * (Illa) (IVa) a source of free radicals for the polymerization of an ethylenically unsaturated monomer. The definitions and preferences of the different substituents have already been mentioned with respect to the initiator compounds. They apply to the other objects of the invention including preferences and individual compounds. The following examples illustrate the invention Example Al: 2, 6-diethyl-2, 3, 6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of acetic acid (Formula 1, Compound 2) To a solution of 6.36 g (2 mmol) of 2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-ol (prepared as described in GB 2335190, Example 7, compound 102) and 2.02 g (2 mmol) of triethylamine in 50 ml of toluene were added 1.57 g (2 mmol) of acetyl chloride at 0-5 ° C and the reaction mixture was stirred for 2 hours at 20 ° C. . The reaction mixture was then extracted several times with water. The organic phase was dried over Na 2 SO 4 and after removing the solvent 6.9 g (96%) of 2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4- were obtained. The acetic acid ester as a yellowish liquid. Elemental analysis calculated for C22H35N03: C 73.0%; H 9.76%; N 3.87%. Found: C 72.87%; H 9.64%; N 3.85%.
Example A2: 2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of acrylic acid (Formula 1, Compound 39) By analogy with Example 1 6.36 g (2 mmol) of 2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-ol were reacted with 1.81 g (2 mmol) of acryloyl chloride and 2.02 g (2 mmol) of triethylamine in toluene to give 6.5 g (87%) of 2,6-di-ethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl. Acrylic acid ester as a yellowish liquid.
Elemental analysis calculated for C23H35N03: C 73.95%; H 9.44%; N 3.75%. Found: C 74.43%; H 9.44%; N 3.91%.
Example A3: 2,6-Diethyl-2, 3,6-trimethyl-1- (1-phenyl-ethoxy) -p? Peridin-4-yl ester of dodecanoic acid (Formula 1, Compound 12) By analogy with the example 1 6.36 g (2 mmol) of 2,6-d? Et? L-2, 3,6-tpmet? Ll- (1-phenyl-ethoxy) -p? Per? D? N-4-ol were reacted with 4.38 g (2 mmol) of lauroyl chloride and 2.02 g (2 mmol) of triethylamine in toluene to give 9.4 g (94%) of 2,6-d? et? l-2, 3, 6-tr ? met? ll- (1-phenyl-ethoxy) -p? pepd? n-4-? l dodecanoic acid ester as a yellowish liquid. Elemental analysis calculated for C32H55N03: C 76.59%; H 11.05%; N 2.79%. Found: C 76.17%; H 11.75%; N 2.69%.
Example A4: 2, 2-diethyl-6,6-dimet? Ll- (1-phenyl-ethoxy) -piperid? N-4-yl ester of dodecanoic acid (Formula Ia, Compound 12) By analogy with Example 1, 6.1 g (2 mmoles) of 2, 2-d? et? l-β, 6-d? met? ll- (1-phenyl-ethoxy) -p? per? dm-4-ol (prepared as is described in GB 2335190, compound 110) with 4.38 g (2 mmol) of chloride of lauroyl and 2.02 g (2 mmoles) of triethylamine and toluene to give 8.9 g (91%) of 2,2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of dodecanoic acid as a yellowish liquid. Elemental analysis calculated for C3? H53 0: C 76. 33%; H 10.95%; N 2.87%. Found: C 75.57%; H 10.92%; N 2.90%.
Example A5: (N- [2,6-Diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -benzamide (Formula 1, Compound 88) A) N- [2,6-Diethyl-2, 3,6-trimethyl-piperidin-l-oxyl-4-yl] -benzamide To a solution of 30.2 g (0.1 mol) of N- [2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl] -benzamide (prepared according to US 4,191,683) in 100 ml of acetate of ethyl, 38 g (0.2 mol) of 40% peracetic acid in acetic acid were added dropwise under cooling with ice. The mixture was stirred for 12 hours at room temperature. The red solution was washed with water, then with 5% NaOH solution and again with water, dried over MgSO4 and concentrated in vacuo. 31.2 g (98%) of N- [2,6-diethyl-2,3, beta-trimethyl-piperidin-1-oxyl-4-yl] -benzamide was obtained as an amorphous solid.
B) In a photoreactor, 150 ml of ethylbenzene, 6.35 g (0.02 mol) of N- [2, ß-d? Et? L-2, 3, 6-tpmet? Lp? Per? Dm-l-ox? l-4-? l] -benzamide and 12.7 g (0.087 mol) of t-butyl peroxide. The red solution was purged with nitrogen and then irradiated with a mercury lamp or a nitrogen atmosphere at 20-25 ° C (pyrex glass). After 8 hours the solution became colorless. The reaction mixture was concentrated under vacuum. The residue was purified by chromatography on silica gel with hexane-ethyl acetate (9: 1) and crystallized from hexane-toluene. 2.53 g (30%) of a colorless solid, mp. 112-147 ° C.
XH-NMR (300 MHz, CDC13): 8.0-7.13 (m, 10 ArH), 6.0-5.85 (m, NH), 4.8-4.65 (m, 1H), 4.65-4.40 (m, 1H), 2.40-0.5 (m, 25H).
Example A6: 1- [2,6-diethyl-2,3,6-trimethyl] -1- (1-phenyl-ethoxy) -piperid? N-4-yl] -3-ethyl-urea (Formula 1, Compound 98 ) A) 1- [2,6-d? Ethyl-2, 3,6-trimet? L-piperidin-l-ox? L-4-yl] -3-ethyl-urea To a solution of 19.8 g (0.1 mol) of 2,6-d? et? l-2, 3, 6-tr? met? lp? per? d? n-4-? l-amma (prepared according to US 4,191,683) in 30 ml of toluene, 7.1 g (0.1 mol) of ethyl ethylisocyanate were added dropwise. The mixture was stirred for 5 hours at room temperature and then concentrated under vacuum. The residue was dissolved in 60 ml of ethyl acetate and 40% peracetic acid was added slowly under cooling with ice water. The mixture was stirred for another 15 hours at room temperature. The red solution was washed with water, then with 5% NaOH solution and again with water, dried over MgSO4 and concentrated or vacuum. 25.65 g (90%) of l- [2,6-d? Et? L-2, 3, 6-tr? Met? Lp? Per? Dm-l-ox? L-4-? L] were obtained. 3-et? L-urea as resinous material.
B) 1.08 g (0.038 mol) of 1- [2,6-d? Et? L-2, 3,6-tr? Met? Lp? Pepd? Nl ~ ox? L-4-? L] were reacted -3-et? L-urea by analogy with Example 5 with ethylbenzene and di-t-butyl peroxide. After chromatographic purification on silica gel with hexane-ethyl acetate (3: 2) 0.7 g (47%) of 1- [2,6-d? Et? L-2, 3,6- tr? met? ll- (1-phenyl-ethoxy) -p? pepd? n-4-? l] -3-et? l-urea as a colorless solid.
XH-NMR (300 MHz, CDC13): 7.4-5.2 (m, 5H), 4.8-4.6 (m, 1H), 4.5-3.9 (m, 3H), 3.3-3.1 (m, 2H), 2.3-0.4 ( m, 18H).
Example A7: 2- [2,6-D? Et? L-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -isoindole-1,3-dione (Formula Compound 111) A) 2- [2,6-Diethyl-2,3,6-trimethyl-piperidin-1-oxyl-4-yl] -isoindole-1,3-dione To a solution of 16.4 g (0.05 mol) of 2- [2,6-d? Et? L-2, 3, 6-tr? Met? Lp? Per? Dm-4-? L] -? Somdol-1 , 3-dαone (prepared according to US 4,191,683) in 50 ml of 1,2-dichlorobenzene were added dropwise 20.6 g (0.1 mole) of 40% peracetic acid or ice cooling. The mixture was stirred for 66 hours at room temperature. The red solution was washed with water, then with 5% NaOH solution and again with water, dried over MgSO4 and concentrated in vacuo. We obtained 16.28g (95%) of 2- [2,6-d? Et? L-2, 3, 6-tpmet? Lp? Pend? Nl-ox? L-4-? L] -isomdol-1, 3-d? Ona like an amorphous solid.
B) 1.54 g (0.0044 mol) of 2- [2,6-d? Et? L-2, 3,6-tr? Met? Lp? Per? Dm-l-ox? L-4? l] -isomodol-1,3-d-one in analogy to example 5 with ethylbenzene and di-t-butyl peroxide. After chromatographic purification on silica gel-ethyl acetate (14: 1), 1.63 g (84%) of 2- [2,6-d? Et? L-2, 3, 6-tr? Met? 11- (1-phenyl-ethoxy) -p? er? d? n-4-? l] -? somdol-1, 3-d? ona as a colorless amorphous solid.
XH-NMR (300 MHz, CDC13): 7.8-7.1 (m, 9H), 4.9-4.5 (m, 1H), 3.3-0.5 (m, 26H).
B) Polymerizations using the initiator / regulator compounds of the formula la General remarks: The solvents and monomers were distilled on a Vigreux column under an argon atmosphere or under vacuum, briefly before being used. To remove the oxygen, all the polymerization reaction mixtures were washed before polymerization with argon and evacuated under vacuum by applying a freeze-thaw cycle. The reaction mixtures were polymerized under an argon atmosphere. At the beginning of the polymerization reaction, all the initial materials were homogeneously dissolved. The conversion was determined by removing the unreacted monomers from the polymer at 80 ° C and 0.002 torr for 30 minutes, weighing the remaining polymer and subtracting the weight of the initiator.
GPC: It was done using a RHEOS 4000 from FLUX INSTRUMENTS. Tetrahydrofuran (THF) was used as the solvent and pumped at 1 ml / min. Two chromatographic columns were placed in series: Plgel type 5μm mixed-C def POLYMER INSTRUMENTS, Shropshire, UK. The measurements were made at 40 ° C. The columns were calibrated with low polydispersity polystyrenes having Mn from 200 to 2,000,000 Daltons.
The detection was carried out using a Rl-ERC-7515A detector from ERCATECH AG at 30 ° C.
Example Bl. Polymerization of the n-butyl acrylate using 1.5 mol% of compound 2 of formula la (example Al) at 145 ° C. In a three-necked 50 ml flask, equipped with thermometer, cooler and magnetic stirrer, 338 mg were mixed and degassed ( 0.94 mmol) of compound 2 and 8 g (62.4 mmoles) of n-butylacrylate the clear solution obtained was heated under argon at 145 ° C and the polymerization was carried out for 5 hours. The reaction mixture was then cooled to 70 ° C. The remaining monomer was removed by evaporation under high vacuum. They also reacted 6.64 g (83%) of the initial monomer. A clear, colorless viscous fluid was obtained.
Mn = 6700, Mw = 8700, PD = 1.3 Example B2 Polymerization of the n-butylacrylate using 1.5 mol% of compound 2 of formula la (example Al) at 130 ° C. In a three-necked 50 ml flask, equipped with thermometer, cooler and magnetic stirrer, 338 mg were mixed and degassed ( 0.94 mmol) of compound 2 and 8 g (62.4 mmoles) of n-butylacrylate. The clear solution obtained was heated under argon at 130 ° C and the polymerization was carried out out for 5 hours. The reaction mixture was then cooled to 70 ° C. The remaining monomer was removed by evaporation under high vacuum. 4.16 g (52%) of the initial monomer also reacted. A clear, colorless viscous fluid was obtained. Mn = 4300, Mw = 5200, PD = 1.2 Example B3. Polymerization of n-butyl acrylate using 1.2 mol% of compound 2 of formula la (example Al) at 145 ° C. In a 50 ml three-necked flask equipped with a thermometer, cooler and magnetic stirrer, 338 mg were mixed and degassed ( 0.94 mmol) of compound 2 and 10 g (62.4 mmoles) of n-butylacrylate. The clear solution obtained was heated under argon at 145 ° C and the polymerization was carried out for 5 hours. The reaction mixture was then cooled to 70 ° C. The remaining monomer was removed by evaporation under high vacuum. 8 g (80%) of the initial monomer also reacted. A clear, colorless viscous fluid was obtained.
Mn = 8500, Mw = 11000, PD = 1.3 Example B Copolymerization of poly (n-butylacrylate) with N, N-dimethylaminoethylacrylate (DMAEA) Into a 50 ml three-necked flask equipped with a thermometer and magnetic stirrer, 6 g of poly (n-butyl-plate) of Example B3 and 6 g (42 mmol) of N, N-dimethylaminoethylamide were mixed and degassed. The clear solution obtained was heated under argon at 145 ° C and the polymerization was carried out for 3.5 h. The remaining monomer was removed by evaporation under high vacuum. They had reacted 2.4 g (40%) of the initial monomer. A light orange viscous fluid was obtained.
Composition (NMR): 65% by weight of butyl acetate / 35% by weight of N, N-dimethylammoethyl acrylate Mn = 13000, Mw = 22150, PD - 1.7

Claims (17)

1. A compound according to the formula o Has characterized because And Y N N O O X (the) where Y is a radical O O O 'I O R1 R2 R, R, O R "O N R < N R, O N O H N N H R x is hydrogen, -COOH, -COO (C 1 -C 4 alkyl), -COO-phenyl, -COO benzyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 4 alkenyl, C? -C18 or C2-C4 alkenyl substituted by OH, -COOH, -COO (C? -C4) alkyl, C2-C? Alkyl, which may be interrupted by one or more oxygen atoms, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or unsubstituted naphthyl; or cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl which are substituted by C 1 -C 4 alkyl, -COOH or -COO- (C 1 -C 4 alkyl) R 2 is hydrogen, C 1 -C 8 alkyl or R x and R 2 together with the nitrogen atom form a 5-membered ring which may have a more saturated bond or be fused to a benzene ring; R3 is hydrogen or C? -C? 8 alkyl; and X is selected from the group consisting of - (C5-C1?.) - 3-c-chloralkenyl, -CH2-phenol, CH3CH-phenyl, (CH3) 2C-phenyl, (C5-C6 cycloalkyl) 2CCN, (CH3) 2CCN, -CH2CH = CH2, CH3CH-CH = CH2 (C 1 -C 4 alkyl) CR 20 -C (0) -phenyl, (C 1 -C 4) alkyl -CR 20 -C (0) -alkoxy (from C 1 -C 4), alkyl (from C 1 -C) -CR20-C (0) -alkyl (from C? ~ C4), alkyl (of C? -C4) -CR20-C (0) -N-dialkyl (of C? -C4), alkyl (from C? -C4) -CR20-C (O) -NH alkyl (from C? -C4), alkyl (from C? -C4) -CR20-C (0) -NH2, where R2o is hydrogen or alkyl ( of C? -C4); with the proviso that 2, ß-d? et? l-2, 3, 6-tpmet? l-1- (1-phenyl-ethoxy) -p? per? dm-4-? l ester is excluded from the benzoic acid. (Anspruch 8, proviso wegen A-21567 spezifisch offenbart)
2. The compound in accordance with the claim 1, characterized in that X is (3-c-Clohexenyl), -CH2-phenol, CH3CH-phenol or (CH3) 2C-phenyl.
3. The compound according to claim 2, characterized in that X is CH3CH-phenyl.
4. The compound according to the formula Ia or Ha, characterized in that Y is a radical of formula
O 0 R1 O ° N ^ Ri and R2 have the meanings H defined in claim 1. 5. A compound, characterized in that it is selected from the group consisting of (1) 2, 6-d? et? l-2, 3, 6-tpmet? ll- (1-phenyl-ethoxy) -p? pepdm-4-formic acid ester; (2) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L acetic acid ester; (3) 2, ß-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L propionic acid ester; (4) 2, ß-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L butyric acid ester; (5) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L pentanoic acid ester; (6) 2, ß-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L hexanoic acid ester; (7) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepd? N-4- l heptanoic acid ester; (8) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L octanoic acid ester; (9) 2, 6-d? Et? L-2, 3,? -tr? Met? L-1- (1-phenyl-ethoxy) -p? Pepdm-4-? L nonanoic acid ester; (10) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-decanoic acid ester; (11) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl undecanoic acid ester; (12) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl ester of dodecanoic acid; (13) 2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4- ll tpdecanoic acid ester; (14) 2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepd? N-4- l tetradecanoic acid ester; (15) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pend? N-4-pentadecanoic acid ester; (16) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepd? N-4-yl hexadecanoic acid ester; (17) 2,6-d? Et? L-2,3,6-tpmet? L-l- (1-phen? L-ethoxy?) -p? Pepd? N-4-heptadecanoic acid ester; (18) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepd? N-4- l-octadecanoic acid ester; (19) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4- l ester methyl ester of carbonic acid; (20) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-ethyl ester ester of carbonic acid; (21) benzyl ester of 2,6,6-d? Et? L-2, 3,6-methyl-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L carbonic acid ester; (22) 2, 6-d? Et? L ~ 2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L carbonic acid ester; (23) 2, 6-d? Et? L-2, 3, ß-tr? Met? L-1- (1-phenyl-ethoxy) -p? Per? D? N-4- l ester methyl ester of oxalic acid; (24) mono- [2, ß-d? Et? L-2, 3, 6-tr? Met? Ll- (1-phenyl-ethoxy) -p? Per? D? N-4-? L] ester of succinic acid; (25) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4- ll ester methyl ester of succinic acid; (26) mono- [2,6-d? Et? L-2, 3,6- tr? Met? Ll- (1-phenyl-ethoxy) -p? Pepdm-4-? L] butyl acid ester 2-end? O? Co; (27) 2, ß-d? Et? L-2, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -p? Pepd? N-4- l ester methyl ester of but-2-end acid ? o? co; (28) mono- [2,6-d? Et? L-2, 3, 6-tr? Met? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? L] acid ester pentandioic; (29) 2, 6-d? Et? L-2, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? L ester methyl ester of pentanedioic acid (30) mono- [2,6-d? et? l-2, 3, 6-tpmet? ll- (1-phenyl-ethoxy) -p? per? dm-4-? l] ester of hexanedioic acid; (31) 2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl ester ester of hexandioic acid; (32) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl ester of cyclohexanecarboxylic acid; (33) 2, 6-d? Et? L-2, 3, 6-tr? Met? Ll- (1-phenyl-ethoxy) -p? Pepd? N-4? -c-clohex-3 acid ester -encarbox? l? co; (34) 2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-benzoic acid ester; (35) 1- [2, 6-d? Et? L-2, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -pipepdm-4-? L] ester of 4-methyl ester of terephthalic acid; (36) 1- [2, 6-d? Et? L-2, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -pipepdm-4-? L] ester of 3-mether ester of isophthalic acid; (37) mono- [2,6-d? Et? L-2, 3,6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L] italic acid ester; (38) 2, ß-d? Et? L-2, 3, 6-tr? Met? Ll- (1-phenyl-ethoxy) -p? Per? D? N-4-l ester of naphthalene-1 acid -carbox? l? co; (39) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4- l ester acrylic acid; (40) 2, 6-d? Et? L-2, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -p? Pepdm-4-l acid ester 2-met? L-acr? L ?co; (41) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-methyl ester of carbamic acid; (42) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-ethyl ester carbamic ester; (43) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4- l ester of isopropyl carbamic acid; (44) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-octadecyl carbamic acid ester; (45) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl ester of cyclohexyl carbamic acid; (46) 2, 6-d? Et? L-2, 3, 6-tr? Met? Ll- (1-phenyl-ethoxy) -p? Per? D? N-4-phenyl carbamic acid ester; (47) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-p-tolylcarbamic acid ester; (48) 2, 6-d? Et? L-2, 3, 6-tr? Met? Ll- (1-phenyl-ethoxy) -p? Pepdm-4-l ester of naphthalene-1? carbam? co; (49) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4- ll dimethyl carbamic acid ester; (50) 2,6-D? Et? L-2,3,6-tr? Met? L-l- (1-phenyl-ethoxy) -piperidin-4-ylamine; (51) N- [2,6-D? Et? L-2, 3,6-t-methyl-l- l- (1-phenyl-ethoxy) -pipepdm-4-? L] -formamide; (52) N- [2,6-D? Et? L-2, 3,6-tr? Met? L-l- (1-phenyl-ethoxy) -pipepdm-4? L] -acetamide; (53) N- [2,6-D? Et? L-2, 3,? -tr? Met? L-1- (1-phenyl-ethoxy) -pipepdm-4-? L] -propionamide; (54) N- [2,6-D? Et? L-2, 3,6-t-methyl-l- (1-phenyl-ethoxy) -piperidm-4-l] -butyramide; (55) [2,6-d? Et? L-2, 3,6-tr? Met? L-l- (1-phenyl-ethoxy) -p? Pepd? N-4-yl] -amide of pentanoic acid; (56) [2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4-yl] -amide of hexanoic acid; (57) [2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of heptanoic acid; (58) [2,6-diethyl-2, 3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of octanoic acid; (59) [2, ß-diethyl-2, 3, 6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of nonanoic acid; (60) [2,6-decathyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of decanoic acid; (61) [2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of undecanoic acid; (62) [2,6-diethyl-2, 3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of dodecanoic acid; (63) [2,6-trityl-2, 3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of tridecanoic acid; (64) [2,6-diethyl-2, 3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of tetradecanoic acid; (65) [2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of pentadecanoic acid; (66) [2,6-hexanedioic acid 2,6-diethyl-2, 3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide; (67) [2, ß-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of heptadecanoic acid; (68) [2,6-diethyl-2, 3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl] -amide of octadecanoic acid; (69) [2, ß-D? Et? I-2, 3, 6-tr? Meth? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? L] - methyl ester carbamic; (70) Ethyl ester of [2,6-D? Et? L-2, 3,6-tnmet? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L] -carbamic acid; (71) Benzyl ester of [2, ß-D? Et? L-2, 3, ß-tr? Met? L-1- (1- phenyl-ethoxy) -p? Per? Dm-4-? L ] -carbamic; (72) Tert-butyl ester of acid [2,6-D? Et? L-2, 3, 6-tr? Met? Ll- (1-f-enyl-ethoxy) -p? Per? D? N-4 -? l] -carbamic; (73) N- [2,6-D? Et? L-2, 3,6- tr? Met? L-l- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] oxaloamic acid; (74) Methyl ester of N- [2,6-D? Et? L-2,3,6-tr? Met? Ll- (1-phenyl-ethoxy) -p? Pepdm-4-? L] - oxalmic; (75) N- [2,6-D? Et? L-2,3,6-methyl-l- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] succinic acid; (76) N- [2,6-D? Et? I-2,3,6-methyl-l- (1- phenyl-ethoxy) -p? Pepdm-4-? L] -succinnamic acid methyl ester; (77) 3- [2, 6-D? Et? L-2, 3, 6-tpmet? L-l- (1-f-enyl-ethoxy) -p? Pepdm-4-? Lcarbamo? L] acrylic acid; (78) 3- [2,6-D? Et? L-2,3,6-tr? Met? Ll- (1- fem-ethoxy) -p? Pepdm-4-? Lcarbamo? ] acrylic; (79) 4- [2,6-D? Et? L-2,3,6-tpmet? L-l- (1-f-enyl-ethoxy) -p? Pepdm-4-? Lcarbamo? L] butyric acid; (80) 4- [2,6-D? Et? L-2,3,6-tpmet? Ll- (1-phenyl-ethoxy) -p? Pepdm-4-? Lcarbamo? L] - methyl ester butyric; (81) 5- [2,6-D? Et? I-2,3,6-methyl-l- (1-phenyl-ethoxy) -p? Pepdm-4-? Lcarbamo? L] pentanoic acid; (82) 5- [2, ß-D? Et? L-2,3,6-tpmet? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? Lcarbamo? ] -pentanoic; (83) N- [2, 6-D? Et? L-2, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -piperidin-4? L] -4-h? Drox? -but ram? da; (84) [2,6-d? Et? L-2, 3,6-tr? Met? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -amide of 6- h? drox? -hexane? co; (85) [2,6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -amide of cyclohexanecarboxylic acid; (86) [2,6-d? Et? L-2, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -amide of c-clohex-3-acid encarboxíl? co; (87) N- [2,6-D? Et? I-2, 3,6-methyl-l- (1-phenyl-ethoxy) -pipepdin-4-? L] -benzamide; (88) N- [2, ß-D? Et? L-2, 3, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? L] methyl ester of acid terephthalamic; (89) N- [2,6-D? Et? L-2, 3, 6-tpmet? Ll- (1-phenyl-ethoxy) -p? Pepd? N-4-? L] methyl ester of isophthalamic acid; (90) N- [2,6-D? Et? L-2,3,6-tr? Met? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? L] phthalamic acid ( 91) [2,6-d? Et? L-2,3,6-tpmet? Ll- (1-phenyl-ethoxy) -p? Per? D? N-4-yl] -amide of naphthalen-1 acid -carboxyl? co; (92) N- [2,6-D? Et? L-2, 3,6-methyl-l- (1-phenyl-ethoxy) -pipepdm-4-? L] -acplamide; (93) N- [2,6-D? Et? L-2, 3,6-tr? Met? Ll- (1-f-enyl-ethoxy) -piperidm-4-? L] -2-met? L -acr? lam? da; (94) N-Butyl-N- [2,6-d? Et? I-2, 3, 6-tpmet? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] -acetamide (95) [2,6-d? et? l-2, 3, 6-tpmet? ll- (1-phenyl-ethoxy) -p? per? dm-4- (96) 1- [2, 6-d? Et? L-2, 3, 6-tr? Met? Ll- (1-f-enyl-ethoxy) -piperidm-4-? L] -3-met? L -urea; (97) 1- [2, 6-d? Et? L-2, 3, 6-tpmet? Ll- (1-f-enyl-ethoxy) -pipendm-4-? L] -3-et? L-urea; (98) 1- [2, 6-d? Et? L-2, 3, 6-tr? Met? Ll- (1-f-enyl-ethoxy) -piperidm-4-? L] -3-? Soprop? l-urea; (99) 1- [2, 6-d? Et? L-2, 3, 6-tr? Met? Ll- (1-f-enyl-ethoxy) -pipepdm-4? L] -3-octadec? -urea; (100) lc? Clohex? L-3- [2, 6-d? Et? L-2, 3, 6-tr? Met? Ll- (1-phenol-ethoxy) -p? Pepdm-4- ? l] -urea; (101) 1- [2, 6-D? Et? L-2, 3, 6-tr? Met? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] -3-f enyl-urea; (102) 1- [2, 6-D? Et? L-2, 3, 6-tpmet? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] -3-. p.-tol? l-urea; (103) 1- [2, 6-D? Et? L-2, 3, 6-tpmet? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] -3-naf talen-1-? l-urea; (104) 3- [2, 6-D? Et? L-2, 3, 6-tpmet? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] -1, 1-d ? met? l-urea; (105) l-But? Ll- [2,6-d? Et? L-2,3,6-tpmet? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] -3-f-enyl-urea; (106) l- [2,6-D? Et? L-2, 3, 6-tpmet? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] -p? Rrol? Dm -2, 5-d? Ona; (107) l- [2,6-D? Et? L-2, 3,6-tr? Met? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] -p ? rrol-2, 5-d? ona; (108) l- [2,6-D? Et? L-2,3,6-tpmet? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] -3.4 -d? met? lp? rrol-2, 5-d? ona; (109) 2 ', 6'-D? Et? L-2', 3 ', 6' -tr? Met? L-1 '- (1-f-enyl-ethoxy) - [1,4'] b? p? per? d? n? l-2, 6 -di ona; (110) 2- [2, 6-D? Et? L-2, 3, 6-tpmet? Ll- (1-f-enyl-ethoxy) -p? Per? D? N-4-? L] -? so-ddol-1, 3-d? ona; (111) 2- [2,6-D? Et? I-2, 3, 6-tr? Met? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] -1 acid, 3-d? Oxo-2, 3-d? H? Dro-l. H. -? somodol-5-carboxylic.
6. A compound, characterized in that it is selected from the group consisting of (1) 2, 2-diethyl-6,6-d? Met? Ll- (1-phen? L-ethoxy?) -p? Pepdm-4- The formic acid ester; (2) 2, 2-d? Et? L-6, 6-d? Met? Ll- (1-phen? L-ethoxy?) -p? Per? D? N-4-? Acetic acid ester; (3) 2, 2-d? Et? L-β, 6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L propionic acid ester; (4) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L-butyric acid ester; (5) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L pentanoic acid ester; (6) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L hexanoic acid ester; (7) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-? L heptanoic acid ester; (8) 2,2-d? Et? L-β, 6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Per? Dm-4-? L octanoic acid ester; (9) 2, 2-diethyl-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L nonanoic acid ester; (10) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L decanoic acid ester; (11) 2, 2-d? Et? L-β, 6-d? Met? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? L undecanoic acid ester, (12) 2 , 2-d? Et? L-6,6-d? Met? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? Ldodecanoic acid ester; (13) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L tpdecanoic acid ester; (14) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L tetradecanoic acid ester; (15) 2, 2-d? Et? L-β, 6-d? Met? L-l- (1-pheny1-ethoxy) -p? Pepdm-4-? L pentadecanoic acid ester; (16) 2, 2-diet 11-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? Lhexadecanoic acid ester; (17) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L heptadecanoic acid ester; (18) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L octadecanoic acid ester; (19) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L methyl ester of carbonic acid; (20) 2, 2-d? Et? L-β, 6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L ester ethyl ester of carbonic acid; (21) benzyl ester of 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L carbonic acid ester; (22) tert.-butyl ester of 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L carbonic acid ester; (23) 2, 2-d? Et? L-6,? -d? Met? L-1- (1-phenyl-ethoxy) -p? Per? Dm-4-? L ester oxalic acid methyl ester; (24) Mono- [2,2-d? Et? L-β, 6-d? Met? L-l- (1-phenyl-ethoxy) -piperidm-4-? L] succinic acid ester; (25) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-? L methyl ester ester of succinic acid; (26) mono- [2, 2-d? Et? L-6, 6-d? Met? Ll- (1-phenyl-ethoxy) -pipendm- 4-? L] acid ester but-2-end? or? co; (27) 2,2-d? Et? L-6,6-d? Met? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? L ester ethyl ester of but-2- acid end? o? co; (28) mono- [2, 2-d? Et? L-β, 6-d? Meth? L-l- (1-fem-ethoxy) -pipepdm-4-? L] ester of pentanedioic acid; (29) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L methyl ester of pentanedioic acid; (30) Mono- [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -piperidm-4? L] ester of hexanedioic acid; (31) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L ester methyl ester of exandioic acid; (32) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L cyclohexanecarboxylic acid ester; (33) 2, 2-d? Et? L-6, 6-d? Met? Ll- (1-phenyl-ethoxy) -p? Pepd? N-4-? L c-clohex-3-acid ester encarboxíl? co; (34) 1- [2, 2-d? Et? L-6,? -d? Met? L-1- (1-phenyl-ethoxy) -piper? D? N-4-yl] ester 4-met The terephthalic acid ester; (35) l- [2,2-d? Et? L -b, 6-d? Met? Ll- (1-phen? L-ethoxy?) -p? Pepdm-4-yl] 3-met ester The isophthalic acid ester; (36) mono- [2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -pipendm- 4-? L] italic acid ester; (37) 2, 2-d? Et? L-6,6-d? Met? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-? L naphthalene-1-carboxylic acid ester? co; (38) 2, 2-d? Et? L-β, 6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-? L acrylic acid ester; (39) 2,2-d? Et? L-6,6-dimet11-1- (1-phen? L-ethoxy?) -p? Per? Dm-4-? L 2-methyl ester? -acr? l? co; (40) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L methylcarbamic acid ester; (41) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L ethyl-carbamic acid ester; (42) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? Isopropylcarbamic acid ester; (43) 2, 2-diethyl-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L octadecyl-carbamic acid ester; (44) 2, 2-d? Et? L-β, 6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L cyclohexylcarbamic acid ester; (45) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L cyclohexylcarbamic acid ester; (46) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L p-tolyl carbamic acid ester; (47) 2, 2-d? Et? L-6,6-d? Met? Ll- (1-phenyl-ethoxy) -p? Per? D? N-4-? L naphthalene-1-acid ester ? l-carbám? co; (48) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L -dimethylcarbamic acid ester; (49) 2,2-D? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-ylamin; (50) N- [2, 2-D? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4-yl] -formamide; (51) N- [2, 2-D? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -acetamide; (52) N- [2, 2-D? Et? L-β, 6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -propionamide; (53) N- [2, 2-D? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -butyramide; (54) [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -amide of pentanoic acid; (55) [2, 2-d? Et? L-β, 6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -amide of hexanoic acid; (56) [2, 2-d? Et? L-6,6-d? Met? Ll- (1-phen? L-ethoxy?) -p? Per? D? N-4-yl] -amide heptanoic acid; (57) [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -amide of octanoic acid; (58) [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -amide, nonanoic acid; (59) [2-et? L-2,6,6-tpmet? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L] -decanoic acid amide; (60) [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -amido of undecanoic acid; (61) [2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-yl] -amido of dodecanoic acid; (62) [2, 2-d? Et? L -b, 6-d? Meth? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -amide of tridecanoic acid; (63) [2, 2-diethyl-6,6-d? Meth? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -amide of tetradecanoic acid; (64) [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -amide of pentadecanoic acid; (65) [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -amide of pentadecanoic acid; (66) [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -amide of hexadecanoic acid; (67) [2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4-yl] -amide of heptadecanoic acid; (68) [2, 2-D? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L] -met-l-carbamic acid ester; (69) [2,2-D? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -pipepdin-4-? L] -et? L ester of carbamic acid; (70) [2,2-D? Et? L-6,6-d? Met? Ll- (1-phen? L-ethoxy?) -p? Per? Dm-4-? L] -benz? Carbamic acid ester; (71) [2, 2-D? Et? L-β, 6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -tert. -carbic acid carbonaceous ester; (72) N- [2, 2-D? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L] oxalolamic acid; (73) N- [2,2-D? Et? L-6,6-d? Met? Ll- (1-phenyl-ethoxy) -p? Pepdm-4-? L] -met? L acid ester oxalmic; (74) N- [2, 2-D? Et? L-6,? -d? Met? L-1- (1-phenyl-ethoxy) -p? Pepdm-4-? L] succmamic acid; (75) N- [2, 2-D? Et? L-6,6-d? Met? Ll- (1-phen? L-ethoxy?) -pipepdm-4-? L] -met? L ester succinic acid; (76) 3- [2, 2-D? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) • p? Per? Dm-4? Lcarbamo? L] acrylic acid; (77) 3- [2, 2-D? Et? L-β, 6-d? Met? Ll- (1-phenyl-ethoxy) -p? Pepdm-4-lcarbamoyl] -ethyl ester of acrylic acid (78 ) 4- [2, 2-D? et? l-6,6-d? met? ll- (1-phenyl-ethoxy) -p? per? dm-4-? lcarbamo? l] butyric acid; (79) 4- [2,2-D? Et? L-6,6-d? Met? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-ylcarbamoyl] -methyl ester of butyric acid; (80) 5- [2,2-D? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? Lcarbamo? L] pentanoic acid; (81) 5- [2,2-D? Et? L-6,6-d? Met? Ll- (1-phen? L-ethoxy?) -p? Per? Dm-4-carbamoyl] -methyl ester of pentanoic acid; (82) N- [2, 2-D? Et? L-6,6-d? Met? Ll- (1-phenyl-ethoxy) -p? Per? D? N-4-yl] -4-h Drox? -but? ram? da; (83) [2, 2-d? Et? L-6,6-d? Meth? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -amide of 6-h? drox? -hexane? co; (84) [2, 2-diethyl-6,6-d? Meth? L-l- (1-phenyl-ethoxy) -p? Per? D? N-4-yl] -amide of cyclohexanecarboxylic acid; (85) [2, 2-d? Et? L-6,6-d? Met? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -amide of c? Clohex- 3-encarbox? L? Co; (86) N- [2, 2-D? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-yl] -benzamide; (87) N- [2, 2-D? Et? L-6,6-d? Met? Ll- (1-phenyl-ethoxy) -p? Pendm-4-? L] -met? L acid ester terephthalamic; (88) N- [2, 2-D? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] -met? L ester talamic isof acid; (89) N- [2, 2-D? Et? L-6,6-d? Met? L-l- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] phthalamic acid; (90) [2, 2-d? Et? L-6,6-d? Meth? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-yl] -amide of naphthalene acid 1-carboxyl; (91) N- [2, 2-D? Et? L-β, 6-d? Met? L-l- (1-f-enyl-ethoxy) -p? Pepdm-4-yl] -acp-lamide; (92) N- [2, 2-D? Et? L-β, 6-d? Met? Ll- (1-f eml-ethoxy) -p? Per? Dm-4-yl] -2-met? l-acplam? da; (93) N-Butyl-.N.- [2,2-d? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? l] -acetamide (94) [2,2-D? et? l-β, 6-d? met? ll- (1-f-enyl-ethoxy) -p? per? dm-4-l!] -urea; (95) 1- [2, 2-D? Et? L-β, 6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-yl] -3-met? L- urea; (96) l-Et? L-3- [2-et? L-2,6,6-tpmet? L-l- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] -urea; (97) l- [2,2-D? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-yl] -3-? Soprop ? l-urea; (98) l- [2,2-D? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-yl] -3-octadec? urea; (99) lC? Clohex? L-3- [2,2-d? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? l] -urea; (100) l- [2,2-D? Et? L-6,6-d? Meth? Ll- (1-phenyl-ethoxy) -p? Per? Dm-4-yl] -3-phenyl-urea; (101) 1- [2,2-Diethyl-6,6-d? Meth? L-1- (1-pheny1-ethoxy) -p? Per? Dm-4-yl] -3-.p. -tolyl-urea; (102) 1- [2, 2-D? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-yl] -3-naphtalene -1-? L-urea; (103) 3- [2, 2-D? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-yl] -1, 1-d? metho-urea; (104) l -But? Ll- [2,2-d? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] -3-f-enyl urea; (105) 1- [2, 2-D? Et? L-6, 6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-yl] -p? Rrol? Dm- 2, 5-d ?one; (106) 1- [2, 2-D? Et? L-6, 6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-yl] -pyrrol- 2, 5-d ?one; (107) 1- [2, 2-D? Et? L-β, 6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-yl] -3, 4- d? met? lp? rrol-2, 5-d? ona; (108) 2 ', 2'-D? Et? L-6', 6 '-dimet 11-1' - (1-f-enyl-ethoxy) - [1,4 '] b? P? Pepd? N? l-2, 6-dione; (109) 2- [2, 2-D? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Pepdm-4-? L] -? So? Ndole-1 , 3-d? Ona; (110) 2- [2,2-D? Et? L-6,6-d? Met? Ll- (1-f-enyl-ethoxy) -p? Per? Dm-4-? L] -1 acid, 3-d? Oxo-2, 3-d? H? Dro-lH-? Somdol-5-carboxylic acid.
7. The compound according to claim 5 or 6, characterized in that it is selected from the group consisting of (1) 2, 6-d? Et? L-2, 3,? -tr? Met? L-1- (1- phenyl-ethoxy) -pipepdm- 4-? l ester of formic acid; (2) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -piperidm- 4-? L acetic acid ester; (3) 2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phen? L-ethoxy?) -piperidm- 4-? L ester of propionic acid; (4) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -piperidm- 4-? L-butyric acid ester; (5) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -piperidm- 4-? L-pentanoic acid ester; (6) 2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -piperidm- 4-? L ester of hexanoic acid; (7) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -pipepdm- 4-? L heptanoic acid ester; (8) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -piperidm- 4-? L octanoic acid ester; (9) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -pipepdm- 4-? L nonanoic acid ester; (10) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -piperidm- 4-? Decanoic acid ester; (11) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phen? L-ethoxy?) -pipepdm- 4-? L undecanoic acid ester; (12) 2, 6-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -pipepdm- 4-? L dodecanoic acid ester; (13) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -piperidm- 4-? Tridecanoic acid ester; (14) 2,6-d? Et? L-2,3,6-tpmet? L-l- (1-phenyl-ethoxy) -pipepdm- 4-? L tetradecanoic acid ester; (15) 2,6-d? Et? L-2,3,6-tpmet? L-l- (1-phen? L-ethoxy?) -piperidm- 4-? L pentadecanoic acid ester; (16) 2, ß-d? Et? L-2, 3, 6-tpmet? L-l- (1-phenyl-ethoxy) -piperidm- 4-? L hexadecanoic acid ester; (17) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -pipepdm- 4-? L heptadecanoic acid ester; (18) 2, 6-d? Et? L-2, 3, 6-tr? Met? L-l- (1-phenyl-ethoxy) -piperidm- 4-? L octadecanoic acid ester; (19) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-? L formic acid ester; (20) 2,2-d? Et? L-6,6-d? Met? Ll- (1-phen? L-ethoxy?) -p? Per? D? N-4-? L acetic acid ester; (21) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? Propionic acid ester; (22) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? -butyric acid ester;
11. (23) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? Pentanoic acid ester; (24) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Per? Dm-4-? Hexanoic acid ester; (25) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? L heptanoic acid ester; (26) 2,2-d? Et? L-β, 6-d? Met? L-l- (1-phen? L-ethoxy?) -pipendin-4-? L octanoic acid ester; (27) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-? L nonanoic acid ester; (28) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-? L decanoic acid ester; (29) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-? L undecanoic acid ester; (30) 2, 2-d? Et? L-β, 6-d? Met? L-l- (1-phenyl-ethoxy) -p? Pepdm-4-? Dodecanoic acid ester; (31) 2,2-d? Et? L-6,6-d? Met? L-l- (1-pheny1-ethoxy) -p? Per? Dm-4-? Tridecanoic acid ester; (32) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-? Tetradecanoic acid ester; (33) 2, 2-d? Et? L-6,6-d? Met? L-l- (1-phenyl-ethoxy) -p? Per? Dm-4-? L pentadecanoic acid ester; (34) 2,2-d? Et? L-6,6-d? Met? L-l- (1-phen? L-ethoxy?) -p? Pepdm-4-? L hexadecanoic acid ester; (35) 2, 2-diethyl-6,6-dimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of heptadecanoic acid; (36) 2,2-diethyl-β, 6-dimethyl-1- (1-phenyl-ethoxy?) -piperidin-4-yl ester of octadecanoic acid; 8. A polymerizable composition, characterized in that it comprises a) at least one ethylenically unsaturated monomer or oligomer, and b) a compound of the formula Ia or Ia. And Y N N O 0 X (the) ("a) where Y is a radical 9 or "o or R? R2 Jl I R R3 I R3 D I1 I O ^ ON 1 N "R, NN 1 ONOH, H Rx is hydrogen, -COOH, -COO (C? -C alkyl), -COO-phenyl, -COO-benzyl, C? -8-alkoxy, C-alkyl? -C? S, C2-C4 alkenyl, C? -C18 alkyl or C2-C4 alkenyl substituted by OH, -COOH, -COO (C? -C4) alkyl, C2-C18 which may be interrupted by one or more oxygen atoms, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or unsubstituted naphthyl; or cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl which are substituted by alkyl of CL-C4, -COOH or -COO- (C? -C4 alkyl) R2 is hydrogen, C? -C18 alkyl or Rx and R2 together with the nitrogen atom they form a 5-membered ring which may have an unsaturated bond or be fused to a benzene ring; R3 is hydrogen or C? -C? Alkyl; and X is selected from the group consisting of - (C5-C12) -3-cycloalkenyl, -CH2-phenyl, CH3CH-phenyl, (CH3) 2C-phenyl, (C5-C6 cycloalkyl) 2CCN, (CH3) 2CCN, - CH2CH = CH2, CH3CH-CH = CH2 (C? -C4 alkyl) CR20-C (O) -phenyl, alkyl (of C? -C4) -CR20-C (O) -alkoxy (of C? -C4) , alkyl (of Cx-C4) -CR2o-C (O) -alkyl (of Cx-C), alkyl (of C? -C4) -CR20-C (0) -N-dialkyl (of C? -C4) , alkyl (of C? -C4) -CR20-C (O) -NH alkyl (of C? -C4), alkyl (of C? -C4) -CR2o_C (O) -NH2, where R2o is hydrogen or alkyl ( of C? -C4); with the proviso that 2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-yl ester of benzoic acid is excluded.
9. The composition according to claim 8, characterized in that the ethylenically unsaturated monomer or oligomer is selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, acidahydrides (alkyl) acrylics, salts of (alkyl) acrylic acid, esters (alkyl) acrylics, (meth) acryl-nitriles, (alkyl) ) acrylamides, vinyl halides or vinyliclene halides. 10. The composition according to claim 8, characterized in that the ethylenically unsaturated monomers are ethylene, propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene, a-alkene
C3-C? 8, styrene, -methyl styrene, p-methyl styrene or a compound of formula CH2 = C (Ra) - (C = Z) -Rb, where Ra is hydrogen or C? -C alkyl, Rb is NH2, O "(Me +), glycidyl, unsubstituted C? -C? Alkoxy, C2-C? Alkoxy or interrupted by at least one N and / or atom, or C? -C? 8 alkoxy, substituted with hydroxy, unsubstituted C? -C? 8 alkylamino, di (C? ~ C18 alkyl) amino, C? -C18 alkylamino substituted by hydroxy or di (C? -C? alkyl) amino substituted by hydroxy, -0-CH2-CH2-N (CH3) 2 or -0-CH2-CH2-N + H (CH3) 2 An "; An "is an anion of a monovalent organic or inorganic acid, Me is a monovalent metal atom or the ammonium ion, Z is oxygen or sulfur.
11. The composition according to claim 8, characterized in that the initiator compound is present in an amount of 0.01 mol% to 30 mol%.
12. A process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically unsaturated monomer or oligomer, characterized in that it comprises (co) polymerizing the monomer or monomers / oligomers in the presence of an initiator compound of formula la or Ha under reaction conditions capable of effecting the cleavage of the OC bond to form two free radicals, the radical * X being capable of initiating the polymerization.
13. The process according to claim 12, characterized in that the cleavage of the bond O-C is carried out by heating and takes place at a temperature between 50 ° C and 160 ° C.
14. A polymer or oligomer, characterized in that it has bound at least one initiator group -X and at least one oxiamine group of formula Ia or Ha according to claim 1.
15. A compound of formula Illa and IVa And Y N N O. O. (Illa) (IVa) characterized because Y is a radical O O O R, R z R, O R, or N R, R, 1 N R., N N R, 1 O 'N O H | H | R x is hydrogen, -COOH, -COO (C 1 -C 4 alkyl), -COO-phenyl, -COO benzyl, C 1 -C 8 alkoxy, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C? -C? 8 or C2-C4 alkenyl substituted by OH, -COOH, -COO (C? -C4) alkyl, C2-C? Alkyl, which may be interrupted by one or more oxygen atoms, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or unsubstituted naphthyl; or cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl which are substituted by C? -C4 alkyl, -COOH or -COO- (C? -C4 alkyl) R2 is hydrogen, C? -Ci8 alkyl or Ri and R2 together with the nitrogen atom they form a 5-membered ring which may have an unsaturated bond or be fused to a benzene ring; R3 is hydrogen or C? -C? 8 alkyl; with the proviso that 2, 6-diethyl-2, 3, 6-trimethyl-4- is excluded lauro? lox? p? per? d? n-1-ox? lo, 2, 6-d? et? l-2, 3, 6-tr? met? l-4-stearo? lox? p? per? d? n-1-oxole, 2, 2-d? met? l-6, 6-d? et? l-4-lauro? lox? p? per? d? n-1-ox? lo and 2, 2-d? Met? L-6, 6-d? Et? L-4-stearoi Lox? P? Per? Dm-1-ox.
16. A polymerizable composition, characterized in that it comprises a) at least one ethylenically ethylenically unsaturated monomer or oligomer, and b) a compound of formula Illa or IVa and c) a source of free radicals capable of initiating the polymerization of ethylenically unsaturated monomers.
17. A process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically ethylenically saturated monomer / oligomer, characterized in that it comprises subjecting the composition according to claim 16. to heat or actinic radiation.
MXPA/A/2001/002660A 2000-03-22 2001-03-14 2,2,6,6-diethyl-dimethyl-1-alkoxy-piperidine compounds and their corresponding 1-oxides MXPA01002660A (en)

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