CA1102335A - 1-oxa-4,8-diazaspiro[4,5]decanes, their production and their use as agents for protection against light - Google Patents
1-oxa-4,8-diazaspiro[4,5]decanes, their production and their use as agents for protection against lightInfo
- Publication number
- CA1102335A CA1102335A CA284,017A CA284017A CA1102335A CA 1102335 A CA1102335 A CA 1102335A CA 284017 A CA284017 A CA 284017A CA 1102335 A CA1102335 A CA 1102335A
- Authority
- CA
- Canada
- Prior art keywords
- oxa
- compound
- carbon atoms
- oxo
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
Abstract of the disclosure:
New 1-oxa-4,8-diazaspiro[4,5]decanes are prepared by react-ing a dimethyl-dialkyl-piperidone with an .alpha.-hydroxyamide in the presence of a condensation catalyst. The compounds can be used as UV stabilizers for polymers.
New 1-oxa-4,8-diazaspiro[4,5]decanes are prepared by react-ing a dimethyl-dialkyl-piperidone with an .alpha.-hydroxyamide in the presence of a condensation catalyst. The compounds can be used as UV stabilizers for polymers.
Description
~l~Z~3S :
,,:. :' The invention relates to new l-oxa-4,8-dlazaspiro ~4,5] decanes, which may be used to protect oryanic materials from the destructive action of ultravio]et light, as well as .
;~ a process for their preparatlon.
The compounds correspond to the~formula H C ~ ~/ R3 (HX)m R
Rl ~ R2 1~ 0 ~
in wl .ch Rl an~R2~re:~the ~r= ~r~different st;aight-chalne1 or:branched alkyl;;radicals:having l to 12 carbon~atoms,~or Rl and R2, together~with the carbon atom to whic~h~they are bonded, form an optionally~methyI-substituted cyc1opentyl, .
: lO cyclohexyl or 2,2,6,6-tetramethylpiperidyl ring, of which the : ;
carbon atom 4 is identical to~the carbon a~tom 9 of the spiro : system. ~::
R3 and R4 are the same or diEferent and represent~hydrogen atoms, alkyl radicals or isoalkyl radicals having l~to 30 : - 2 - . :
",~
' -,. . .
:", .. ...
- : -- - ~ ,: ,, : ~ . ; . :
' ~ ' "' ' ' ' ' ' ' 233~
carhon atoms or represent aryl radicals having 6 to 10 carbon atorns optionally suh-titu-ted by a halogen atom or by an alkyl radical having 1 to 4 carbon atorns, or aralkyl radicals having 7 to 10 carbon atoms, or R3 and R4 together with the carbon atom to which ~hey are bonded, form a cycloalkyl cJroup having 4 to 20 carbon atoms, which may be subs-tituted by Cl -to C4 alkyl groups, or an optionally alkyl-substituted pyrrolidine or piperi.dine group, the ring nitro~en a-tom of which cannot be in the ~-position to the spiro atom, R5 represents a hydrogen atom, an oxygen atom o the hyclroxyl group or an alkyl group having 1 to 4 carbon atoms, and HX represents a non-oxidizing mineral acid or an aliphatic or aromatic sulfonic or phosphonic acid, an aliphatic mono-, di- or polycarboxylic acid or an aromatic mono-or dicarboxylic acid and _ = 0 or 1 but when ~ N-R5 does not have a basi.c reaction, is always 0.
Examples o~ the 7,7-dimethyl-9,9-dialkyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decanes are, ~or example~
,,:. :' The invention relates to new l-oxa-4,8-dlazaspiro ~4,5] decanes, which may be used to protect oryanic materials from the destructive action of ultravio]et light, as well as .
;~ a process for their preparatlon.
The compounds correspond to the~formula H C ~ ~/ R3 (HX)m R
Rl ~ R2 1~ 0 ~
in wl .ch Rl an~R2~re:~the ~r= ~r~different st;aight-chalne1 or:branched alkyl;;radicals:having l to 12 carbon~atoms,~or Rl and R2, together~with the carbon atom to whic~h~they are bonded, form an optionally~methyI-substituted cyc1opentyl, .
: lO cyclohexyl or 2,2,6,6-tetramethylpiperidyl ring, of which the : ;
carbon atom 4 is identical to~the carbon a~tom 9 of the spiro : system. ~::
R3 and R4 are the same or diEferent and represent~hydrogen atoms, alkyl radicals or isoalkyl radicals having l~to 30 : - 2 - . :
",~
' -,. . .
:", .. ...
- : -- - ~ ,: ,, : ~ . ; . :
' ~ ' "' ' ' ' ' ' ' 233~
carhon atoms or represent aryl radicals having 6 to 10 carbon atorns optionally suh-titu-ted by a halogen atom or by an alkyl radical having 1 to 4 carbon atorns, or aralkyl radicals having 7 to 10 carbon atoms, or R3 and R4 together with the carbon atom to which ~hey are bonded, form a cycloalkyl cJroup having 4 to 20 carbon atoms, which may be subs-tituted by Cl -to C4 alkyl groups, or an optionally alkyl-substituted pyrrolidine or piperi.dine group, the ring nitro~en a-tom of which cannot be in the ~-position to the spiro atom, R5 represents a hydrogen atom, an oxygen atom o the hyclroxyl group or an alkyl group having 1 to 4 carbon atoms, and HX represents a non-oxidizing mineral acid or an aliphatic or aromatic sulfonic or phosphonic acid, an aliphatic mono-, di- or polycarboxylic acid or an aromatic mono-or dicarboxylic acid and _ = 0 or 1 but when ~ N-R5 does not have a basi.c reaction, is always 0.
Examples o~ the 7,7-dimethyl-9,9-dialkyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decanes are, ~or example~
2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2-ethyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2-propyl-7r7t9r9-tetramethyl-l-oxa-3-oxo-4r8-diazaspiro[4r5]decane 2--butyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2-isobutyl-7,7,9,9-tetramethyl-1-oxa-4,8-diazaspiro[4,5]decane 2-pentyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8-diazasprio[4,5]decane 2-isopentyl-7,7,9,9-tetramethyl-1-oxa-3~oxo-4,8-diazaspiro[4,5]decane 2-isoheptyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8-diazasplro[4,5]decane -2-phenyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,3-diazaspiro[4,5idecane 2,2,.7,7,9,9--hexamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane : . 2,2-diethyl~7,7,9,9-tetramethyl-1-oxa-3-oxo~4,8-diazaspiro[4,5]decane 2,2-dipropyl-7,7,9,9--tetramethyl-1-oxa-3-oxo-4,8-diazasplro[4,5]decane ~ _ 3 _ ~"
;
2,2-~ibutyl-7,7,9,9--tetramethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2~2-dipentyl-7~7~9~9-tetramethy~ oxa-3-oxo-4~8-diazaspiro[4~5]decane 2-ethyl-2,7,7,9,9-pentamethyl-1-oxa-3--oxo-4,8-diazasprio[4,5]decane 2-propyl-2,7,7,9,9-pen-tamethyl-1-oxa--3-oxo-4,8-diazasprio[4,5]decane 2--isopropyl-2l7~7~9~9-pentamethyl-l-oxa-3-oxo-4~8-diazaspiro[4~5]decane 2-butyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2-isobutyl-2~7~7/9/g-pentamethyl-l-oxa--3--oxo-4/8-diazaspiro[4/5]decane ~ :
2-pentyl-2,7,7,9,9~?entamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5~decane 2-isopentyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2-hexyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2-heptyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diaza~spiro[4,5]decane ~
2-nonyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane ~. .
2-undecyl-2,7,7,9,9-pentamethyl--1-oxa-3-oxo-4,~-diazasprio[4,5]decane 2-ethyl-2-butyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8~iazasprio[4,5]decane ;:
2-ethyl-2-pentyl 7,7,9,9-tetramethyl-1-oxa-3-oxo-4j8-diazaspiro[4,5]decane 2-ethyl-2-isopentyl-7,7,9,9--tetramethyl-1-oxa-3-oxo-4,8-diazasprio[4,5]decane 2,7,7,9,9-pentamethyl~ oxa-3-oxo-4,8-diaza-8-oxylsprlo[4,5]decane 2-hexyl-2,7,7,9,9-pentamethyl-1-oxa-3--oxo-4,:8-diaza-8-oxylsprio `~
~; ~ [4,5]decane ~ ~ :
2,2-diethyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8-diaza-8 oxylspiro [4,5]decane 2,2,4,4,-te-tramethyl-7-oxa-13-oxo-3,14-diazadisprio[5,1,4,2]
tetradecane 2,2,4,4 tetramethyl-7-oxa-14-oxo-3,15-diazadisprio[5,1,5,2]pentadecane ~:
2~2l4~-tetramethyl-7-oxa-~o-oxo-ll2l-diazadizpriols~ 2lhenel osa e ' ,, ' ... , ., . ~ , The different nomenclature of the last three com-pounds is derived from the IUPAC regulations (cf. Hellwinkel "Die systematische Nomenklatur der Oryanischen Chemie", Springer-Verlag, Heidelberg). ~ ~-The sprio compounds of the invention in which m =
0 and R5 ~ H are ob-tainable by means of a condensation reaction between a 2,2-dimethyl-6,6-dialkylpiperidone, or a salt thereof, and a ~-hydroxyamide in accordance with the following reaction equation:
3t/ ~ ~ OH ~ ~
Rl 2 CONH2 n ~1 O ~:i Rl, R , R3 and R4 havlng the meanl~ngs given above.
The reaction is advantageously carried out in an oryanic solvent, preferably a lower aliphatic carboxylic acid and especially in glacial acetic acid, in the`presence of a water-removing agent, such as, for example, polyphosphoric acid, or preferably sulfuric acid. ~he reaction temperature is 20 to 180, preferably 40 to 120 and especially 50 to 80C.
When using glacial acetic acid as solvent, equimolar amounts of piperidone and ~-hydroxyamide are introduced into 3 to 10 times the amount by weight of glacial acetic acid and calculated on piperidone twice, or when the ~-hydroxyamide contalns a basic centre three times, the molar amount of concentrated sulfuric acid is added dropwise, whereuponthe mixture is heated. The reaction temperature selected may be between 40 and 120C. In the course of-the - '' ~:
~z33~
the reaction the sulfuric acid ~alts of the compounds of the invention are generally precipitated, o-therwise the mixture must be concentrated. The free bases are obtained from the salts so produced, by treating with ammonia or alkali hydroxide solu-tion, and these bases may be converted, preferably in an organicsolvent or water, into the salts of inorganicand organic acids.
The compounds, in which m = 0 and R5 - H, may be alkylated with alkyl halides, preferably alkyl bromides or iodides. The methyl -group may also be introduced by reacting with formic acid and aqueous formaldehyde solution, CO2 being split off. By treating the compounds in which R5 = ~ with hydrogen peroxide, compounds in which R = 0 are produced.
The 2,2-dimethyl-6,6-dialkylpiperidones used as starting compounds can be produced according to methods known per se (for -~
example, Beilstein, Volume 21, page 249; German Offenlegungs-schrift No. 1 695 753); the ~-hydroxyamides~are obtained ln accordance with the following reaction scheme:
:
= O + HCN ---~ ~ + H20 -~ ~ ~
R4 / R ~ \ 4 CONH ~`
The two reaction~steps can be carried out according to known processes. To hydrolyse the cyanohydrine, acids, pre-ferably sulfuric acid, to which a quantity of water equimolar tothe cyanohydrin has been added, or alkaline H2O2 (Houben-Weyl, Methoden der organischem Chemie, 4th Edition, Volume 3, pages 662-663) may be used. An especially suitable process is carried out by way of the imino ether hydrochlorides in accordance with the following reaction equation:
,; - ,
;
2,2-~ibutyl-7,7,9,9--tetramethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2~2-dipentyl-7~7~9~9-tetramethy~ oxa-3-oxo-4~8-diazaspiro[4~5]decane 2-ethyl-2,7,7,9,9-pentamethyl-1-oxa-3--oxo-4,8-diazasprio[4,5]decane 2-propyl-2,7,7,9,9-pen-tamethyl-1-oxa--3-oxo-4,8-diazasprio[4,5]decane 2--isopropyl-2l7~7~9~9-pentamethyl-l-oxa-3-oxo-4~8-diazaspiro[4~5]decane 2-butyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2-isobutyl-2~7~7/9/g-pentamethyl-l-oxa--3--oxo-4/8-diazaspiro[4/5]decane ~ :
2-pentyl-2,7,7,9,9~?entamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5~decane 2-isopentyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2-hexyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane 2-heptyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diaza~spiro[4,5]decane ~
2-nonyl-2,7,7,9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]decane ~. .
2-undecyl-2,7,7,9,9-pentamethyl--1-oxa-3-oxo-4,~-diazasprio[4,5]decane 2-ethyl-2-butyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8~iazasprio[4,5]decane ;:
2-ethyl-2-pentyl 7,7,9,9-tetramethyl-1-oxa-3-oxo-4j8-diazaspiro[4,5]decane 2-ethyl-2-isopentyl-7,7,9,9--tetramethyl-1-oxa-3-oxo-4,8-diazasprio[4,5]decane 2,7,7,9,9-pentamethyl~ oxa-3-oxo-4,8-diaza-8-oxylsprlo[4,5]decane 2-hexyl-2,7,7,9,9-pentamethyl-1-oxa-3--oxo-4,:8-diaza-8-oxylsprio `~
~; ~ [4,5]decane ~ ~ :
2,2-diethyl-7,7,9,9-tetramethyl-1-oxa-3-oxo-4,8-diaza-8 oxylspiro [4,5]decane 2,2,4,4,-te-tramethyl-7-oxa-13-oxo-3,14-diazadisprio[5,1,4,2]
tetradecane 2,2,4,4 tetramethyl-7-oxa-14-oxo-3,15-diazadisprio[5,1,5,2]pentadecane ~:
2~2l4~-tetramethyl-7-oxa-~o-oxo-ll2l-diazadizpriols~ 2lhenel osa e ' ,, ' ... , ., . ~ , The different nomenclature of the last three com-pounds is derived from the IUPAC regulations (cf. Hellwinkel "Die systematische Nomenklatur der Oryanischen Chemie", Springer-Verlag, Heidelberg). ~ ~-The sprio compounds of the invention in which m =
0 and R5 ~ H are ob-tainable by means of a condensation reaction between a 2,2-dimethyl-6,6-dialkylpiperidone, or a salt thereof, and a ~-hydroxyamide in accordance with the following reaction equation:
3t/ ~ ~ OH ~ ~
Rl 2 CONH2 n ~1 O ~:i Rl, R , R3 and R4 havlng the meanl~ngs given above.
The reaction is advantageously carried out in an oryanic solvent, preferably a lower aliphatic carboxylic acid and especially in glacial acetic acid, in the`presence of a water-removing agent, such as, for example, polyphosphoric acid, or preferably sulfuric acid. ~he reaction temperature is 20 to 180, preferably 40 to 120 and especially 50 to 80C.
When using glacial acetic acid as solvent, equimolar amounts of piperidone and ~-hydroxyamide are introduced into 3 to 10 times the amount by weight of glacial acetic acid and calculated on piperidone twice, or when the ~-hydroxyamide contalns a basic centre three times, the molar amount of concentrated sulfuric acid is added dropwise, whereuponthe mixture is heated. The reaction temperature selected may be between 40 and 120C. In the course of-the - '' ~:
~z33~
the reaction the sulfuric acid ~alts of the compounds of the invention are generally precipitated, o-therwise the mixture must be concentrated. The free bases are obtained from the salts so produced, by treating with ammonia or alkali hydroxide solu-tion, and these bases may be converted, preferably in an organicsolvent or water, into the salts of inorganicand organic acids.
The compounds, in which m = 0 and R5 - H, may be alkylated with alkyl halides, preferably alkyl bromides or iodides. The methyl -group may also be introduced by reacting with formic acid and aqueous formaldehyde solution, CO2 being split off. By treating the compounds in which R5 = ~ with hydrogen peroxide, compounds in which R = 0 are produced.
The 2,2-dimethyl-6,6-dialkylpiperidones used as starting compounds can be produced according to methods known per se (for -~
example, Beilstein, Volume 21, page 249; German Offenlegungs-schrift No. 1 695 753); the ~-hydroxyamides~are obtained ln accordance with the following reaction scheme:
:
= O + HCN ---~ ~ + H20 -~ ~ ~
R4 / R ~ \ 4 CONH ~`
The two reaction~steps can be carried out according to known processes. To hydrolyse the cyanohydrine, acids, pre-ferably sulfuric acid, to which a quantity of water equimolar tothe cyanohydrin has been added, or alkaline H2O2 (Houben-Weyl, Methoden der organischem Chemie, 4th Edition, Volume 3, pages 662-663) may be used. An especially suitable process is carried out by way of the imino ether hydrochlorides in accordance with the following reaction equation:
,; - ,
3~S
R3 OH ~ OH :E~ OH
~ -~ CH30H + VCl ~ ca.80-120C~
R CN ,, 3 R CClNH2 NH . HCl The imino ether hydrochloride does not, however, need to be puri-fied before the pyrolysis.
There are limits imposed upon the synthesis of the -new l-oxa-4,8-diazaspiro[4,5]decanes since it is not as easy to product the ~-hydroxyamides from long-chained carbonyl compounds as it is from short-chained carbonyl compounds.
Suitable compounds for the production of the hydroxyamides to be used are, for example, those that can be ob-tained from the cyanohydrins of the following carbonyl compounds~
formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso- ~
butyraldehyde, valeraldehyde, isovaleraldehyde, capronaldehyde, ~`~:--2-ethylbutyraldehyde, oenanthaldehyde, 2-ethylcapronaldehyde, caprylaldehyde, pelargonaldehyde, isononylaldehyde, caprinaldehyde, ~
isodecylaldehyde, laurlnaldehyde, benzaldehyde, hydrocinnamaldehyde, ~ :
also acetonej methyl ethyl ketone, methyl propyl ketone, methyl -~
isopropyl ketone, haxan-2-one, methyl isobutyl ketone, methyl isopropyl ketone, haxan-2-one, methyl isobutyl ketone, heptan-2-one, heptan-3-one, heptan-4-one, octan-2-one, octan-2-one, nonan-2-one, nonan-5-one, undecan-6-one, tridecan-2-one, methyl isopentyI
ketone, ethyl isopentyl ketone, diethyl ketone, diben~yl ketone~
cyclopentanone, cyclohexanone, cyclododecanone, benzophenone, acetophenone, propiophenone.
In the new compounds of the formula ;~
~,~J' .
, .
, ~ .
, 2;~3~i (IlX) R5 N~ R4 Rl and R~ represent straight-chained or - but not in the ~-position to the heterocycle - branched alkyl groups having l to 12, preferably 1 to 6 carbon atoms. Rl and R2 may be the same or different. The compounds in which Rl and R2 represent methyl, which may be derived from readily obtainable triacetone-amine, are especially important. Further, Rl and R2 together with the carbon atom 9 to which they are bonded, form an optionally methyl-substituted cyclopentane or cyclohexane ring, or represent a 2,26,6-tetramethylpiperidine group of which the carbon atom ;~
in the 4-position is the spiro atom.
Examples of Rl are methyl and of R2 methyl, isobutyl or hexyl, of Rl and R together with~the carbon atom 9 bonding them cyclopentyl, cyclohexyl and~2,2,6,6-tetramethylpiperidyl.
The radicals R3 and R4 stem for the ~-hydroxyamides used, axe the same or different and represent hydrogen, straight-chained or branched alkyl groups having 1 to 30 carbon atoms, an optionally halogen-substituted, preferably chlorine-substituted or alkyl-substitued (wherein the alkyl group may consist of l to
R3 OH ~ OH :E~ OH
~ -~ CH30H + VCl ~ ca.80-120C~
R CN ,, 3 R CClNH2 NH . HCl The imino ether hydrochloride does not, however, need to be puri-fied before the pyrolysis.
There are limits imposed upon the synthesis of the -new l-oxa-4,8-diazaspiro[4,5]decanes since it is not as easy to product the ~-hydroxyamides from long-chained carbonyl compounds as it is from short-chained carbonyl compounds.
Suitable compounds for the production of the hydroxyamides to be used are, for example, those that can be ob-tained from the cyanohydrins of the following carbonyl compounds~
formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso- ~
butyraldehyde, valeraldehyde, isovaleraldehyde, capronaldehyde, ~`~:--2-ethylbutyraldehyde, oenanthaldehyde, 2-ethylcapronaldehyde, caprylaldehyde, pelargonaldehyde, isononylaldehyde, caprinaldehyde, ~
isodecylaldehyde, laurlnaldehyde, benzaldehyde, hydrocinnamaldehyde, ~ :
also acetonej methyl ethyl ketone, methyl propyl ketone, methyl -~
isopropyl ketone, haxan-2-one, methyl isobutyl ketone, methyl isopropyl ketone, haxan-2-one, methyl isobutyl ketone, heptan-2-one, heptan-3-one, heptan-4-one, octan-2-one, octan-2-one, nonan-2-one, nonan-5-one, undecan-6-one, tridecan-2-one, methyl isopentyI
ketone, ethyl isopentyl ketone, diethyl ketone, diben~yl ketone~
cyclopentanone, cyclohexanone, cyclododecanone, benzophenone, acetophenone, propiophenone.
In the new compounds of the formula ;~
~,~J' .
, .
, ~ .
, 2;~3~i (IlX) R5 N~ R4 Rl and R~ represent straight-chained or - but not in the ~-position to the heterocycle - branched alkyl groups having l to 12, preferably 1 to 6 carbon atoms. Rl and R2 may be the same or different. The compounds in which Rl and R2 represent methyl, which may be derived from readily obtainable triacetone-amine, are especially important. Further, Rl and R2 together with the carbon atom 9 to which they are bonded, form an optionally methyl-substituted cyclopentane or cyclohexane ring, or represent a 2,26,6-tetramethylpiperidine group of which the carbon atom ;~
in the 4-position is the spiro atom.
Examples of Rl are methyl and of R2 methyl, isobutyl or hexyl, of Rl and R together with~the carbon atom 9 bonding them cyclopentyl, cyclohexyl and~2,2,6,6-tetramethylpiperidyl.
The radicals R3 and R4 stem for the ~-hydroxyamides used, axe the same or different and represent hydrogen, straight-chained or branched alkyl groups having 1 to 30 carbon atoms, an optionally halogen-substituted, preferably chlorine-substituted or alkyl-substitued (wherein the alkyl group may consist of l to
4 carbon atoms) aryl radical having 6 or 10 carbon atoms or an aralkyl radical having 7 to lO carbon atoms, of which l to 4 carbon atoms belong to the aliphatic chain.
Depending on whether the ~-hydroxyamide used was pro-duced from aldehyde or ketone, the following are preferred for R3 3~,3 and R .
If ~--hydroxyamides synthesized from aldehycles are used, R3 is hydrogen whereas R4 may be hydrogen, or an alkyl group having 1 to 30, preferably 1 to 17 and especially 1 to 11 carbon atoms. Further, R4 may be an aryl radical having 6 to ].0 carbon atoms (phenyl or naphthyl) optionally substituted by a halogen .-atom - preferably chlorine - or by an alkyl radical having -1 to 4 carbon atoms, or an aralkyl radical having 7 to 10 carbon atoms, wherein 1 to 4 carbon atoms belong to the aliphatic chain.
~hen using a ~-hydro~yamide obtained from a ketone, R3 is an alkyl group having 1 to 30, preferably 1 to 10 and especially 1 to 6 carbon atoms or an aralkyl radical having . :-7 to 10 carbon atoms, wherein the aliphatic chain has 1 to 4 .-carbon atoms. R4 is in this case an alkyl radical;having 1 to 30, preferably 1 to 17 and especially 1 to 11 carbon atoms, or ~`
an aryl radical having 6 to 10 carbon atoms optionally substituted by a halogen atom- preferably chlorine - or by an alkyl radical having 1 to 4 carbon atoms, or an aralkyl radical having 7 to 10 carbon atoms, wherein the a].iphatic chain consists of 1 to 4 carbon atoms.
Examples o radicals R3 are hydro~en, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, ;~
nonyl, decyl, undecyl, heptadecyl, benzyl, phenylethyl, and of radicals R4, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 25 2-ethylbutyl, pentyl, isopentyl, 2-ethylpentyl, isohexyl, pentyl, isoheptyl, octyl, issoctyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, 4-iso-propylphenyl, 4-methylbenzyl, pehnyl, phenylethyl, 2-chlorophenyl, :: _ g _ ~ ~ , , .;
: ' . ' :~, . ' ' , 3-chlorophenyl, 4-chlorophenyl, l-naphthyl, 2-naphthyl and benzyl.
R3 and ~4 may, finally, -toyether with the carbon atom to which they are bonded, form cycloalkyl group having 4 to 20, preEerably 5 to 12 and especially 5 to 7 carbon atoms.
The cycloalkyl group here may be substituted by Cl to C4-alkyl radicals. R3 and R4 may together with the carbon atom to which they are bonded for an optionally alkyl-substituted pyrrolidine or piperidine ring. The ring nitrogen atom in this may not be in the ~-position to the spiro atom. Examples of rings formed by the incorporation of the spiro atom are cyclopentyl, 3`methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, cycloheptyl, cyclo-octyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclopentadency and piperidyl.
The radical RS is preferably hydrogen.; It may also be the oxygen atom of a hydroxyl group or an alkyl group having l to 4 carbon atoms.
HX represents an inorganic or organic acid. The following may be mentioned: non-oxidizing mineral acids, ali-phatic sulfonic or phosphonic acids having 1 to 30, preferably l to 18 carbon atoms~ optionally alkylated aromatic sulfonic or phosphonic acids having 6 to 25, preferably 6 to 18 carbon atoms, wherein l to 3 alkyl grou~s having 1 to 16 carbon atoms may be present, further, aliphatic, straight-chained or branched mono- or dicarboxylic acids having 2 to 34, preferably 2 to 18 carbon atoms, or optionally also aliphatic polycarboxylic acids having up to 4 carboxyl groups and a total of up to 16 carbon ,-~; ,i - 1 0 - - ~.
,: :
~Z~35 atoms, or also aromatic, optionally Cl - to C4-alkyl- or isoalkyl-substituted mono- or dicarboxylic acids having 7 to 25, preferably 7 to 19 carbon atoms.
The following are mentioned in particular: phosphorie acid and phorphorous acid, sulfuric acid, phenylphosphonie acid, camphorsulfonic acid, dodecylsulfonic acid-p~toluenesulfonie acid, alkylpolyglycolethersulfonie aeid, alkarylpolyglyeolether-sulfonie aeid, acetie acid, propionic aeid, oetanoie aeid, 2-ethylhexanoie aeid, laurie aeid, stearic acid, tallow fatty acid, montanic acid, suecinic acid, adipic acid, azelaie acid, citric acid, tricarballyl acid, benzoic aeid, tolyl acids, p-tert.~butylbenzoie acid, phthalic acid and terephthalic acid.
That the invention relates both to free bases and to the abo~e-mentioned salts, or in -the case of polybasic acids optionally also to aeid salts of 1-oxa-4,8-diazaspiro[4,5]decanes, is indieated in the general formula by m being 0 to I. In eom-pounds in which the group ~N-R5 is not eapable of salt formation, -~ ~
m is 0.
The l-oxa 4,8~diazaspiro[4,5]deeanes aceording to the invention impart to organic polymer compositions an extraordinary stability towards deeomposition by~the aetion of heat, and espeeially by ultraviolet radiation. Apart from the faet that the compounds in which R5 = O have a typical natural color (yellow to orange-red), the color properties of the organic polymer compositions are not impaired. In this property they are superior to the sterically hindered piperidine compounds which are ~nown as excellent W stabilizers, sueh as, for ~-example, triacetone-amine, some of whieh tend towards de-composition and/or discoloring when heated. The new compounds . ' :
s are particularly valuable for the liyht stabilization of polyolefins, such as, for example, polyisoprene, polybutadiene, polystyrene and especially polypropylene and polyethylene of low and hiyh densi-ty, also ethylene/propylene copolymers, ethylene/butene copolymers, ethylene/vinyl acetate copolymers, styrene/butadiene copolymers and acrylonitrile/styrene/butadiene copolymers.
Other organic polymers are polyvinyl chloride, polyvinyl acetate and copolymers of the corresponding monomers with other olefinically unsaturated monomers. The term organic polymer also includes, for example, polyacetals, polyesters, polyamides, polyacrylates, polyurethanes and epoxy resins.
The quantity of new compounds to be added to the organic polymers can vary considerably, depending on the type the properties and special uses of the polymer to be stabilized.
For most uses, ~.01 to 5 parts by weightt preferably 0.05 to 3 parts be weight, especially 0.1 to 1.5 parts by weight, cal~
culated on the amount of synthetlc polymer, are employed. One compound or a mixture of several compounds can be used.
The compounds according to the invention are ln-corporated into the organic polymer compositions according to customary methods. Thus, the stabilizer can be mixed in the form of a powder with the polymer. Alternatively, a solution, suspension or emulsion of the stabilizer can be incorporated into the polymer directly or into solution, suspension or emulsion of the same, the solvent beiny subsequently removed.
, , -The stabllizers are effectlve .i.n their own or in admixture with one or more customary stabilizers, such as, for example, antioxidants, based on phenol and sulfide, UV-absorbers and agents for protection against light, phosphite stabilizers, metal compounds peroxide decomposing agents, epoxy stabilizers, polyhydric alcohols and also together antistatic agents, flame-proofing agents and pigments.
Examples of suitable antioxidants are those of the sterically hindered phenol type, such as 2,6-di-t.-butyl-p-kresol, 1,6-di-octadecyl-p-kresol, 4,4'-butylidene-bis (2,6-di-t.-butylphenol), 4,4'-thio-bis-(2-t.-butyl-5-methylphenol), phenolic triazine compounds, triodipropionic acid esters of fatty alcohols, dioctadecyl sulfide and disulfide.
The W absorbers and agents for protection against ~-15 light include, for example 2-(2'-hydroxyphenyl)-benztriazoles, such as, 2-(2'~hydroxy-5'-methylphenyl)-benztriazole, 2-hydroxy-benzophenones such as 2-hydroxy-4-octoxybenzophenone, stabilizers from the group salizylates, such as octylphenyl salizylate, nickel chelates and oxalic acid diamides.
rrrisnonylphenyl phospite, trislauryl phosphite or also esters of pentaerythritol phosphite may be mentioned as phosphites. ;~`
By metal compounds known as stabilizers there are to be understood in this connection: calcium barium strontium, zinc, cadmium, magnesium, aluminium and lead soaps of alipahtic carboxylic acids of hydroxycarboxylic acids having approximately 12 to 32 carbon atoms, salts of the mentioned metals with ~, ' ' ' ' ' ', .
, 3~
aromatic carboxylic acids, such as benzoates or sallzylates as well as (alkyl-)phenolates of these metals, also organotin compounds, such as, for example dialkyltine thioglycolates and carboxylates.
Known epoxy stabilizers, are, for example, epoxidized higher fatty acids, such as epoxidized soya bean oil, tall oil, linseed oil or opozidized butyloleate as well as opoxides of long-chained a-olefins.
Polyhydric alcohols may be, for example, pent-aerythritol, trimethylol propane, sorbitol or mannitol, that is, preferably alcohols having 5 or 6 carbon atoms and 3 to 6 OH groups.
An effective stabilizer combination for poly-a-olefins, such as for example, hlgh, medium and low pressure polymers of C2 to C4-~-olefins, especially polyethylene and polypropylene, or of copolymer~s of such ~-olefins consists, based on 100 parts by weight of polymer, for example of 0.01 ~:
to 5 parts by weight of one of the compounds to be used according to the invention, 0.05 to 5 parts by weight of a phenolic stabilizer, optionally 0.01 to 5 parts by weight of a sulfur-contalning~costabilizer, as well as, optionally, 0.01 to 3 parts by weight of a basic or neutral metal soap, such as, for example, calcium stearate or zinc stearate, as well as, optionally, 0.1 to 5 parts by weight of a phosphite ~5 and optionally 0.01 to 5 parts by weight of a known W
stabilizer from the yroup alkoxyhydroxybenzophenones, hydroxy-phenylbenzotriazoles, benzylidenamalonic acid mononitrile .
., ," : , : ', ' .
, .. . . .
.. . .
esters or the so-called quenchers such as nlckel chelates.
In the following the process for -the production of the new compounds is illustrated by way of a few examples and the excellent efficiency of the same as agents for protectiny plastics compositions against light is demonstrated.
_arnple 1 _ 7,7,9,9-Pentamethyl-l-oxa-3-oxo-4,8-diazaspiro~4,5]decane 31.0 g (0.2 mole) of triacetone-amine and 17.8 g (0.2 mole) of lactic acid amide are in-troduced into 200 g of glacial acetic acid, Then 43.1 g (0.44 mole) of concentrated H2SO4 are added dropwise while stirring, whereupon heating at 60~C is carried out for 40 hours. The precipitate formed on -cooling is filtered off with suction (35 g ^- 54% of the theore-tical yield of the sulfuric~acid sa~lt of the desired compound), dissolved in approximately 50 ml of water and stirred into 100 ml of concerntrated NH3. The desired compound is pre-cipitated in the course of this. It is filtered of with suction and recrystallized Erom acetone. Mp 215C.
Examples 2 to 7 The following were prepared analogously to ; Rxample 1 from equimolar amounts of triacetone-amine and ~-hydroxyamide:
-.
- ,, , ; - . ~ , ~ - :
, ' ,:
~ -Example Ccmpound ~-hydroxyamide Product ~p C
No. used in which crystallized R3 = R = from _ ._ 2 2-e-thyl-2,7,7,9'9~ CH3C2H5 ethanol 237 pentamethyl-l-oxa-3-oxo-4,8-diazaspiro [4,5]decane 3 2-isopropyl-2,7,7, CH3i-C3H7 methanol 241-242 9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]-decane ~H3 4 2-isobutyl-2,7,7, CH3CH2 methanol 218-219 9,9-pentamethyl-1- CH
oxa-3-oxo-4,8-di- 3 azaspiro[4,5]-decane .
2,2-diethyl-7,7,9,9- C2H5 C2H5 ethanol 254 tetramethyl-l ~xa-2-oxo-4,8-diazaspiro [4,5]decane ~
6 2,2,4,4-tetramethYl- (C~12)4 ethanol 249 7-oxa-13-oxo-3,14-diazadispiro[5,1,4,2]
tetradecane 7 2,2,4,4-tetramethyl- (CH2j5 ethanol 276 7-o~a-14-oxo-3,15-diazadispir~ :
[5,1,5,2] Ferbad~cane , _ __ _ , Ex~nple 8 2-Ethyl-7,7,9,9-tetram~thyl-1-oxa-3-oxo-4,8-dl~zasplro[4,5]decane 46.5 g (0.3 mole) of triacetone-amine and 30.9 g ;
(0.3 mole) of 2-hydroxybutyramide are introduced into 300 y of glacial acetic acid. 62.7 (0.64 mole) of concentrated H2SO4 are added dropwise while stirring. Stirring is then continued , ,.l .
.
for 20 hours at 80C. The glacial acetic acid is then dis-til]ed off _ vacuo and the residue is stirred with ether/
acetone. The precipitate produced is suction-filtered off, dissolved in 100 ml of water and stirred into 150 ml of con-centrated NH3. The precipitated compound is suction~filtered off and recrystallized from acetone. Mp. 196C. -Examples 9 to 11 The following were prepared analogously to Examp]e 8:
~Example Compound ~-hydroxyallLide Product Mp. ~C
No. used in which cr stallized 9 2-phenyl-7,7,9,9- H 6 5 ethanol 222-223 tetr~methyl-l-oxa -3-ox~4,8 diasa-sprio[4,5]decane 2-isoheptyl-7,7,9, H i-C7H15 ethyl acetate 168 9-tetramethyl-1-oxa-3-oxo~4,8-dia- ~-zaspiro[4,5]decane 11 2,2-dipentyl-7,7,9,CSHll ~C5Hll ethyl acetate 2:13-215 9-tetramethyl-1-oxa-3-oxo-4,8-dia-zasprio[4,5]decane _ ' - 16a- ;
:
':
'~' ' . - . - : ~' :' . ' ~ . ' - ' ',: . ., ;. - . . . . . . .
'' " ' ' ~ ' ' ' : ' ' , . . ' , 2 Propyl 7,7,9,9-tetrameth~ o2a-3-o~o-4~8~diazaapiro~4,5~decanc 77~5 g (0.5 mole) of triacetone-amine and 58~3 g (0.5 mol~) o~
2-hydro~yvaleramide are introduoed lnto 500 g o~ glacial acetic acid. 107.8 g (1.1 mole) oi co~oentrated H2S04 are then added dropwi~e ~hile ~tirrlng a~d the whols is then stirred ~or 72 hours Pt 60Cr The glacial acetic acid ~g the~ distilled o~f u~der slightl~ reduced pressure~ the oily residue i~ dis~olYed i~ ~ater and stirred into concentrated NH~. The substance precipitated i9 uction-filtered o~f Pnd recrystallized from ethanol. Mp. 199C.
2DBut~1~7,7t9,9-tetramethylw1-oxa-3 o~o-4,8-diaza~piro[4,5]deca~s The preparation o~ this compound i3 carried out analogousl~ to E~ample 8 with ~9.3 g ~0~3 mole) oY 2-h~dro~ycapronamide instaad o~ 2-hydro~butyramide ~or a period o~ 72 hours and at a tempePature o~ 60C. The produc~ is recrystallized irom methanolO Mp. 182C.
~ ,.
:
The follo~ing compo~d~ were produced in accordanoe with Ezample 13:
, .
~2~35 EX.~mple CcmpoNnd ~-hydroxyamide Product Mp C
No. used in wh'ch crystallized 14 2-isobutyl-7,7,9, H CH3 ethyl 206-107 9-tetramethyl-1- / acetate cxa-3-oxo-4,8- CH2.CEI
diazaspiro[4,5] \CH
decane 3 2-pentyl-2,7,7,9, CH3C5Hll methanol186-188 9-pentamethyl-1-oxa-3-oxo-4,8-dia-zaspiro[4,5]decane 16 2-nonyl-2,7,7,9,9- CH3CgHlg acetone/164-166 pentamethyl-l-oxa- water 2-oxo-4,8-diaza-spiro[4,5]decane 17 2-ethyl-2-isopen- C2H5i-C5Hll acetone 208 tyl-7,7,9,9-tetra-methyl-l-oxa-2-oxo 4,8-diazaspiro[4,5]
decane : : :
Æxample 18 2-Isopentyl-7/7~9~9-tetramethyl-l-oxa-3-oxo-4/8-diazaspiro[4~s]decane ~;
The preparation is carried out analogously to Æxample 13.
When the reaction is complete approximately 100 ml of ethe~ is added.
The sulfuric acid salt of the desired compound then crystallizes out and after suction filtration is worked up analogously to Æxample 1. Mp. (ethyl acetate) 223-224C.
~' ~
~" .
','' ,'' ~ ~.
.' . - ', .''..
: ', ' ' ' . ' ' ' ' ' ' , .: ' ' , ~he :~llowing were produced in aocordance with ~3xample 18:
_._ , _ . _ ~ample ~ompound a-hydro~yamide Product ~p o~
No~ used i~ whlch crystal R3- R4= lized ~rom _ . . _ _ . . _ . . _ 19 2-butyl 2, 7, 7 ~ 9, CH C4H aoetone/ 199-200 9; pentamethyl- 1- 3 9 water oxa-3-oxo-4, 8-diazaspiro [ 4, 5 ]
decane 2-i~opentyl2~7, ~H CH ethyl 199 7~9,9-pentamethyl 3 / 3 acetate -1-ox~ o~o-4~8- ~C~2)~C~
diaza~piro~4,5J . \ :::
r~c~ ~E~ ~ _ .~ .
:
-~ 2,2~7,7,9,9-He~amethyl-l-o~a-~-o~o-4,8-diazaspiro~4,5]deoans ~ he pr~paration of this compound i3 carried out analr:~gou8~ y to B~ample 1~, usin~ 77.5 g (005 mole) o~ triacetone-Rmine and Q~5 mole of 2-h~dro~gisobutyramide~ The sul~uric acid salt o~ th~
; desired compound i8 precipitated during the reaction and i9 suction-~iltered o~. Yield: 118 g ^- 70 % of the theoretical ~ield.
Mp. (methanol) 2~8C.
Exam~les 2~2 to ~
~ he prooedure 1~ a~ in Example 21 and the ~ollowing producte are obtained:
:' : ~g ' . ' ~ . ' ~ .
. ~ .
.; .
Exa~ple Compound ~hydroxy~mide cr~stal- Mp C
R3- R4= lized ~rom __ ____ 22 2-pent~1-7,7,9, H C ~ ethanol 215 9-tetramethyl- 5 11 1-o~a~3-oxo-4g 8~diazaspiro~4,
Depending on whether the ~-hydroxyamide used was pro-duced from aldehyde or ketone, the following are preferred for R3 3~,3 and R .
If ~--hydroxyamides synthesized from aldehycles are used, R3 is hydrogen whereas R4 may be hydrogen, or an alkyl group having 1 to 30, preferably 1 to 17 and especially 1 to 11 carbon atoms. Further, R4 may be an aryl radical having 6 to ].0 carbon atoms (phenyl or naphthyl) optionally substituted by a halogen .-atom - preferably chlorine - or by an alkyl radical having -1 to 4 carbon atoms, or an aralkyl radical having 7 to 10 carbon atoms, wherein 1 to 4 carbon atoms belong to the aliphatic chain.
~hen using a ~-hydro~yamide obtained from a ketone, R3 is an alkyl group having 1 to 30, preferably 1 to 10 and especially 1 to 6 carbon atoms or an aralkyl radical having . :-7 to 10 carbon atoms, wherein the aliphatic chain has 1 to 4 .-carbon atoms. R4 is in this case an alkyl radical;having 1 to 30, preferably 1 to 17 and especially 1 to 11 carbon atoms, or ~`
an aryl radical having 6 to 10 carbon atoms optionally substituted by a halogen atom- preferably chlorine - or by an alkyl radical having 1 to 4 carbon atoms, or an aralkyl radical having 7 to 10 carbon atoms, wherein the a].iphatic chain consists of 1 to 4 carbon atoms.
Examples o radicals R3 are hydro~en, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, ;~
nonyl, decyl, undecyl, heptadecyl, benzyl, phenylethyl, and of radicals R4, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 25 2-ethylbutyl, pentyl, isopentyl, 2-ethylpentyl, isohexyl, pentyl, isoheptyl, octyl, issoctyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, 4-iso-propylphenyl, 4-methylbenzyl, pehnyl, phenylethyl, 2-chlorophenyl, :: _ g _ ~ ~ , , .;
: ' . ' :~, . ' ' , 3-chlorophenyl, 4-chlorophenyl, l-naphthyl, 2-naphthyl and benzyl.
R3 and ~4 may, finally, -toyether with the carbon atom to which they are bonded, form cycloalkyl group having 4 to 20, preEerably 5 to 12 and especially 5 to 7 carbon atoms.
The cycloalkyl group here may be substituted by Cl to C4-alkyl radicals. R3 and R4 may together with the carbon atom to which they are bonded for an optionally alkyl-substituted pyrrolidine or piperidine ring. The ring nitrogen atom in this may not be in the ~-position to the spiro atom. Examples of rings formed by the incorporation of the spiro atom are cyclopentyl, 3`methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, cycloheptyl, cyclo-octyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclopentadency and piperidyl.
The radical RS is preferably hydrogen.; It may also be the oxygen atom of a hydroxyl group or an alkyl group having l to 4 carbon atoms.
HX represents an inorganic or organic acid. The following may be mentioned: non-oxidizing mineral acids, ali-phatic sulfonic or phosphonic acids having 1 to 30, preferably l to 18 carbon atoms~ optionally alkylated aromatic sulfonic or phosphonic acids having 6 to 25, preferably 6 to 18 carbon atoms, wherein l to 3 alkyl grou~s having 1 to 16 carbon atoms may be present, further, aliphatic, straight-chained or branched mono- or dicarboxylic acids having 2 to 34, preferably 2 to 18 carbon atoms, or optionally also aliphatic polycarboxylic acids having up to 4 carboxyl groups and a total of up to 16 carbon ,-~; ,i - 1 0 - - ~.
,: :
~Z~35 atoms, or also aromatic, optionally Cl - to C4-alkyl- or isoalkyl-substituted mono- or dicarboxylic acids having 7 to 25, preferably 7 to 19 carbon atoms.
The following are mentioned in particular: phosphorie acid and phorphorous acid, sulfuric acid, phenylphosphonie acid, camphorsulfonic acid, dodecylsulfonic acid-p~toluenesulfonie acid, alkylpolyglycolethersulfonie aeid, alkarylpolyglyeolether-sulfonie aeid, acetie acid, propionic aeid, oetanoie aeid, 2-ethylhexanoie aeid, laurie aeid, stearic acid, tallow fatty acid, montanic acid, suecinic acid, adipic acid, azelaie acid, citric acid, tricarballyl acid, benzoic aeid, tolyl acids, p-tert.~butylbenzoie acid, phthalic acid and terephthalic acid.
That the invention relates both to free bases and to the abo~e-mentioned salts, or in -the case of polybasic acids optionally also to aeid salts of 1-oxa-4,8-diazaspiro[4,5]decanes, is indieated in the general formula by m being 0 to I. In eom-pounds in which the group ~N-R5 is not eapable of salt formation, -~ ~
m is 0.
The l-oxa 4,8~diazaspiro[4,5]deeanes aceording to the invention impart to organic polymer compositions an extraordinary stability towards deeomposition by~the aetion of heat, and espeeially by ultraviolet radiation. Apart from the faet that the compounds in which R5 = O have a typical natural color (yellow to orange-red), the color properties of the organic polymer compositions are not impaired. In this property they are superior to the sterically hindered piperidine compounds which are ~nown as excellent W stabilizers, sueh as, for ~-example, triacetone-amine, some of whieh tend towards de-composition and/or discoloring when heated. The new compounds . ' :
s are particularly valuable for the liyht stabilization of polyolefins, such as, for example, polyisoprene, polybutadiene, polystyrene and especially polypropylene and polyethylene of low and hiyh densi-ty, also ethylene/propylene copolymers, ethylene/butene copolymers, ethylene/vinyl acetate copolymers, styrene/butadiene copolymers and acrylonitrile/styrene/butadiene copolymers.
Other organic polymers are polyvinyl chloride, polyvinyl acetate and copolymers of the corresponding monomers with other olefinically unsaturated monomers. The term organic polymer also includes, for example, polyacetals, polyesters, polyamides, polyacrylates, polyurethanes and epoxy resins.
The quantity of new compounds to be added to the organic polymers can vary considerably, depending on the type the properties and special uses of the polymer to be stabilized.
For most uses, ~.01 to 5 parts by weightt preferably 0.05 to 3 parts be weight, especially 0.1 to 1.5 parts by weight, cal~
culated on the amount of synthetlc polymer, are employed. One compound or a mixture of several compounds can be used.
The compounds according to the invention are ln-corporated into the organic polymer compositions according to customary methods. Thus, the stabilizer can be mixed in the form of a powder with the polymer. Alternatively, a solution, suspension or emulsion of the stabilizer can be incorporated into the polymer directly or into solution, suspension or emulsion of the same, the solvent beiny subsequently removed.
, , -The stabllizers are effectlve .i.n their own or in admixture with one or more customary stabilizers, such as, for example, antioxidants, based on phenol and sulfide, UV-absorbers and agents for protection against light, phosphite stabilizers, metal compounds peroxide decomposing agents, epoxy stabilizers, polyhydric alcohols and also together antistatic agents, flame-proofing agents and pigments.
Examples of suitable antioxidants are those of the sterically hindered phenol type, such as 2,6-di-t.-butyl-p-kresol, 1,6-di-octadecyl-p-kresol, 4,4'-butylidene-bis (2,6-di-t.-butylphenol), 4,4'-thio-bis-(2-t.-butyl-5-methylphenol), phenolic triazine compounds, triodipropionic acid esters of fatty alcohols, dioctadecyl sulfide and disulfide.
The W absorbers and agents for protection against ~-15 light include, for example 2-(2'-hydroxyphenyl)-benztriazoles, such as, 2-(2'~hydroxy-5'-methylphenyl)-benztriazole, 2-hydroxy-benzophenones such as 2-hydroxy-4-octoxybenzophenone, stabilizers from the group salizylates, such as octylphenyl salizylate, nickel chelates and oxalic acid diamides.
rrrisnonylphenyl phospite, trislauryl phosphite or also esters of pentaerythritol phosphite may be mentioned as phosphites. ;~`
By metal compounds known as stabilizers there are to be understood in this connection: calcium barium strontium, zinc, cadmium, magnesium, aluminium and lead soaps of alipahtic carboxylic acids of hydroxycarboxylic acids having approximately 12 to 32 carbon atoms, salts of the mentioned metals with ~, ' ' ' ' ' ', .
, 3~
aromatic carboxylic acids, such as benzoates or sallzylates as well as (alkyl-)phenolates of these metals, also organotin compounds, such as, for example dialkyltine thioglycolates and carboxylates.
Known epoxy stabilizers, are, for example, epoxidized higher fatty acids, such as epoxidized soya bean oil, tall oil, linseed oil or opozidized butyloleate as well as opoxides of long-chained a-olefins.
Polyhydric alcohols may be, for example, pent-aerythritol, trimethylol propane, sorbitol or mannitol, that is, preferably alcohols having 5 or 6 carbon atoms and 3 to 6 OH groups.
An effective stabilizer combination for poly-a-olefins, such as for example, hlgh, medium and low pressure polymers of C2 to C4-~-olefins, especially polyethylene and polypropylene, or of copolymer~s of such ~-olefins consists, based on 100 parts by weight of polymer, for example of 0.01 ~:
to 5 parts by weight of one of the compounds to be used according to the invention, 0.05 to 5 parts by weight of a phenolic stabilizer, optionally 0.01 to 5 parts by weight of a sulfur-contalning~costabilizer, as well as, optionally, 0.01 to 3 parts by weight of a basic or neutral metal soap, such as, for example, calcium stearate or zinc stearate, as well as, optionally, 0.1 to 5 parts by weight of a phosphite ~5 and optionally 0.01 to 5 parts by weight of a known W
stabilizer from the yroup alkoxyhydroxybenzophenones, hydroxy-phenylbenzotriazoles, benzylidenamalonic acid mononitrile .
., ," : , : ', ' .
, .. . . .
.. . .
esters or the so-called quenchers such as nlckel chelates.
In the following the process for -the production of the new compounds is illustrated by way of a few examples and the excellent efficiency of the same as agents for protectiny plastics compositions against light is demonstrated.
_arnple 1 _ 7,7,9,9-Pentamethyl-l-oxa-3-oxo-4,8-diazaspiro~4,5]decane 31.0 g (0.2 mole) of triacetone-amine and 17.8 g (0.2 mole) of lactic acid amide are in-troduced into 200 g of glacial acetic acid, Then 43.1 g (0.44 mole) of concentrated H2SO4 are added dropwise while stirring, whereupon heating at 60~C is carried out for 40 hours. The precipitate formed on -cooling is filtered off with suction (35 g ^- 54% of the theore-tical yield of the sulfuric~acid sa~lt of the desired compound), dissolved in approximately 50 ml of water and stirred into 100 ml of concerntrated NH3. The desired compound is pre-cipitated in the course of this. It is filtered of with suction and recrystallized Erom acetone. Mp 215C.
Examples 2 to 7 The following were prepared analogously to ; Rxample 1 from equimolar amounts of triacetone-amine and ~-hydroxyamide:
-.
- ,, , ; - . ~ , ~ - :
, ' ,:
~ -Example Ccmpound ~-hydroxyamide Product ~p C
No. used in which crystallized R3 = R = from _ ._ 2 2-e-thyl-2,7,7,9'9~ CH3C2H5 ethanol 237 pentamethyl-l-oxa-3-oxo-4,8-diazaspiro [4,5]decane 3 2-isopropyl-2,7,7, CH3i-C3H7 methanol 241-242 9,9-pentamethyl-1-oxa-3-oxo-4,8-diazaspiro[4,5]-decane ~H3 4 2-isobutyl-2,7,7, CH3CH2 methanol 218-219 9,9-pentamethyl-1- CH
oxa-3-oxo-4,8-di- 3 azaspiro[4,5]-decane .
2,2-diethyl-7,7,9,9- C2H5 C2H5 ethanol 254 tetramethyl-l ~xa-2-oxo-4,8-diazaspiro [4,5]decane ~
6 2,2,4,4-tetramethYl- (C~12)4 ethanol 249 7-oxa-13-oxo-3,14-diazadispiro[5,1,4,2]
tetradecane 7 2,2,4,4-tetramethyl- (CH2j5 ethanol 276 7-o~a-14-oxo-3,15-diazadispir~ :
[5,1,5,2] Ferbad~cane , _ __ _ , Ex~nple 8 2-Ethyl-7,7,9,9-tetram~thyl-1-oxa-3-oxo-4,8-dl~zasplro[4,5]decane 46.5 g (0.3 mole) of triacetone-amine and 30.9 g ;
(0.3 mole) of 2-hydroxybutyramide are introduced into 300 y of glacial acetic acid. 62.7 (0.64 mole) of concentrated H2SO4 are added dropwise while stirring. Stirring is then continued , ,.l .
.
for 20 hours at 80C. The glacial acetic acid is then dis-til]ed off _ vacuo and the residue is stirred with ether/
acetone. The precipitate produced is suction-filtered off, dissolved in 100 ml of water and stirred into 150 ml of con-centrated NH3. The precipitated compound is suction~filtered off and recrystallized from acetone. Mp. 196C. -Examples 9 to 11 The following were prepared analogously to Examp]e 8:
~Example Compound ~-hydroxyallLide Product Mp. ~C
No. used in which cr stallized 9 2-phenyl-7,7,9,9- H 6 5 ethanol 222-223 tetr~methyl-l-oxa -3-ox~4,8 diasa-sprio[4,5]decane 2-isoheptyl-7,7,9, H i-C7H15 ethyl acetate 168 9-tetramethyl-1-oxa-3-oxo~4,8-dia- ~-zaspiro[4,5]decane 11 2,2-dipentyl-7,7,9,CSHll ~C5Hll ethyl acetate 2:13-215 9-tetramethyl-1-oxa-3-oxo-4,8-dia-zasprio[4,5]decane _ ' - 16a- ;
:
':
'~' ' . - . - : ~' :' . ' ~ . ' - ' ',: . ., ;. - . . . . . . .
'' " ' ' ~ ' ' ' : ' ' , . . ' , 2 Propyl 7,7,9,9-tetrameth~ o2a-3-o~o-4~8~diazaapiro~4,5~decanc 77~5 g (0.5 mole) of triacetone-amine and 58~3 g (0.5 mol~) o~
2-hydro~yvaleramide are introduoed lnto 500 g o~ glacial acetic acid. 107.8 g (1.1 mole) oi co~oentrated H2S04 are then added dropwi~e ~hile ~tirrlng a~d the whols is then stirred ~or 72 hours Pt 60Cr The glacial acetic acid ~g the~ distilled o~f u~der slightl~ reduced pressure~ the oily residue i~ dis~olYed i~ ~ater and stirred into concentrated NH~. The substance precipitated i9 uction-filtered o~f Pnd recrystallized from ethanol. Mp. 199C.
2DBut~1~7,7t9,9-tetramethylw1-oxa-3 o~o-4,8-diaza~piro[4,5]deca~s The preparation o~ this compound i3 carried out analogousl~ to E~ample 8 with ~9.3 g ~0~3 mole) oY 2-h~dro~ycapronamide instaad o~ 2-hydro~butyramide ~or a period o~ 72 hours and at a tempePature o~ 60C. The produc~ is recrystallized irom methanolO Mp. 182C.
~ ,.
:
The follo~ing compo~d~ were produced in accordanoe with Ezample 13:
, .
~2~35 EX.~mple CcmpoNnd ~-hydroxyamide Product Mp C
No. used in wh'ch crystallized 14 2-isobutyl-7,7,9, H CH3 ethyl 206-107 9-tetramethyl-1- / acetate cxa-3-oxo-4,8- CH2.CEI
diazaspiro[4,5] \CH
decane 3 2-pentyl-2,7,7,9, CH3C5Hll methanol186-188 9-pentamethyl-1-oxa-3-oxo-4,8-dia-zaspiro[4,5]decane 16 2-nonyl-2,7,7,9,9- CH3CgHlg acetone/164-166 pentamethyl-l-oxa- water 2-oxo-4,8-diaza-spiro[4,5]decane 17 2-ethyl-2-isopen- C2H5i-C5Hll acetone 208 tyl-7,7,9,9-tetra-methyl-l-oxa-2-oxo 4,8-diazaspiro[4,5]
decane : : :
Æxample 18 2-Isopentyl-7/7~9~9-tetramethyl-l-oxa-3-oxo-4/8-diazaspiro[4~s]decane ~;
The preparation is carried out analogously to Æxample 13.
When the reaction is complete approximately 100 ml of ethe~ is added.
The sulfuric acid salt of the desired compound then crystallizes out and after suction filtration is worked up analogously to Æxample 1. Mp. (ethyl acetate) 223-224C.
~' ~
~" .
','' ,'' ~ ~.
.' . - ', .''..
: ', ' ' ' . ' ' ' ' ' ' , .: ' ' , ~he :~llowing were produced in aocordance with ~3xample 18:
_._ , _ . _ ~ample ~ompound a-hydro~yamide Product ~p o~
No~ used i~ whlch crystal R3- R4= lized ~rom _ . . _ _ . . _ . . _ 19 2-butyl 2, 7, 7 ~ 9, CH C4H aoetone/ 199-200 9; pentamethyl- 1- 3 9 water oxa-3-oxo-4, 8-diazaspiro [ 4, 5 ]
decane 2-i~opentyl2~7, ~H CH ethyl 199 7~9,9-pentamethyl 3 / 3 acetate -1-ox~ o~o-4~8- ~C~2)~C~
diaza~piro~4,5J . \ :::
r~c~ ~E~ ~ _ .~ .
:
-~ 2,2~7,7,9,9-He~amethyl-l-o~a-~-o~o-4,8-diazaspiro~4,5]deoans ~ he pr~paration of this compound i3 carried out analr:~gou8~ y to B~ample 1~, usin~ 77.5 g (005 mole) o~ triacetone-Rmine and Q~5 mole of 2-h~dro~gisobutyramide~ The sul~uric acid salt o~ th~
; desired compound i8 precipitated during the reaction and i9 suction-~iltered o~. Yield: 118 g ^- 70 % of the theoretical ~ield.
Mp. (methanol) 2~8C.
Exam~les 2~2 to ~
~ he prooedure 1~ a~ in Example 21 and the ~ollowing producte are obtained:
:' : ~g ' . ' ~ . ' ~ .
. ~ .
.; .
Exa~ple Compound ~hydroxy~mide cr~stal- Mp C
R3- R4= lized ~rom __ ____ 22 2-pent~1-7,7,9, H C ~ ethanol 215 9-tetramethyl- 5 11 1-o~a~3-oxo-4g 8~diazaspiro~4,
5]decane.
23 2-propyl-2,7,7, a~ a X7 ethanol 212 9,9-pentamethyl 3 3 -l-oxa-3-o~o-4, 8-diaza~piro[4, 5]decane.
24 2-hex~1 2,7,7, CH3 C6H~3 ethanol 191-192 9,9-pentameth~l -1 -sxa-3-oxo-4, 8~diazaspiro[4~5]
-decane.
2-hsptyl-2,7,7, C~ C H eth~l 187-188 ~g-pe~ta~ethyl-1 3 7 15 acetate o~a-2-o~o-4,8-diazaspiro[4,5~-decane, 26 2-undecyl-2~7,7,CH3 C11 23 ethyl 166 9,9-pentamethyl- aoetate 1-o~a-2-c~o-4,8~
:~ dia~aæp~ roE4 ~ 5]~
.~ decane.
; 27 2-~thyl-2 butyl- a H c~ ~9 ethyl 213 7,7,9,9~tetra- 2 5 4 acetate ~ methyl-1-oxa-2- .
: oxo-4 ~diaza-~piro~4,5]decan~, . :
~ 2B 2-ethyl~2-pentylC2~ C H1 eth~l 198-199 :. .
: -7,7,9,9~tetra- 5 5 1 acetate methyl-1-o~a-2-oxo-4 8-diaza~
.; 8 piro~4,5~decane.
29 2~2-diprop~1-7,7,3 7 3 7 ethanol 242-243 9,9-tetramethyl- .
1-oxa-2-oxo-4,8-diazaspiro[4~5]-: decane.
2~2-dibutyl-7,7,C4H9 C4H9 ethyl 225 .~ 9~9-tetramethyl- acetate 1~oxa-3-o~o-4,8-:. '.' diazaspiro[4,5]-. . decane~
__ ~ ,. ., , - 20 _ - , .-. . : , -.
, ~ . . .
~ .
, . .: , , ~1~233 .
2~2,474 Tetramethyl-7-oxa 20-oxo-3,21-diazaspiro~5,1,1172]heneioosane 45~5 g (0.3 mole) o~ triacetone-amine and 68~1 g (0.3 mole) of l-hydroxycyclodod~oane carbo~amide are lntroduced into 300 g o~
glacial acetic acid~ 62.7 g t0.64 mole) of concentrated H2~04 are added while stirring9 Stirring is continued ~or 15 hours at 70C and a~ter cooling the reaction ml~ture, the sul~uric ac~d salt of the desired compound is ~uctio~-filtered of~ Yield: 81 g = 59 ~ o~ the theoretical yield. ~he salt is dissolved in ethanol/water with heating, the solu~ion i8 stirred into concentrated aqueou~ a~monia, tha precipi-tated amine base i~ cuction~filtered off and rec~ystallized from cyclohe~a~on~0 The crystals are ~a~hed wlth ether. Mp. 273Co ~2 ~15 2 9 7,7,9,9-Pe~tamethy~ oxa-3-oxo-4,8-diaza~8-o~Ylspiro[4~5]decane 5 g of the compou~d according to E~ample 1, 50 ml of methanol, 9 ml ~ 3 ~ ~22~ 002 g of ~a2SO~ and 0.2 g of ethylenedi~mine tetraacetic acid are heated ~or 48 hour~ at 60C. Concentratio~
in ~Q~e is carried out, not to drgne~s, 20 ml o~ water i8 added~
suction-filtering is e~fected ~ollowed by recrystallization ~rom acetone/heptane, 3.5 g of orange-colored c~y~tals are obtai~ed.
Mp. 170~1 72Co . - 21 -:
The following were produced analogously to E~ample ~2:
_, .. _ _ .__ : ~x~mple Starting product Produot Mp C
No. Compound according to crystal-E~ample lized ~rom . .
_~ ___ ; 33 2-hexyl-2 9 7,7,9, 24 ether 112-113 9-pentameth~
oxa-3-oxo-4,8-dia-za-8-oxylspiro-C4,5]decane : ~4 2,2-diethyl 7.719~ 5 heptane/ 128-130 9-tetramethyl-1- acetone oxa-3-oxo-4,8-di-aza-8-oxylspiro-:~ -~4,5]decane .
~_ _ ___ '''' '''' : .. , . ~
2,2,7g7,8,9,9-heptsmethyl-1-ox~ 3-o~o~4,8-diazaspiro[4~5]deoane ::~
, ~5 24~0 g of the compound a¢cording to ~ample 21 are introduced into 256 g o~ 90 % ~o~mlc acidO i62 g of 37 ck formaldeh~de 801ution are added dropwise over a period o~ one hour, while stirring, at 20 to ~0C~ ~he mi~ture is heated slowlg to reflux and boiled until C2 evolution is complete (appro~i stely 15 hvurs). The formic acid is then distilled off a~d, after cooling, the residue is stirred into concentrated aqueous smmo~ia~ 15 ~ of white crystals having a melting point of 205 to 207C are precipitated~ -., '~' ,, ~' . , ".
, , , . :, .
~2~3 ~
2-Isobutyl~2,7,7,~,9,9-hexamethyl-1~oxa-3-oxospiro[4,5]decane ~his compound was obtained as in the above Example from 28~2 g of the product of Example 4~ Mp. 138C.
:
~k~Y~
2-He~yl 2,7,7,9,9-pentamethyl 1-oxa-3 oxo-4,8-dia~aspiro~4~5]decane p-ter~utylbenzoate 3.10 g (0.01 mole) of the compound according to Example 24 ~nd 1.78 g (0.01 mole) o~ p-tert~ butylbenzoio aoid are heated ~or 15 10 minutes in 20 ml of methanol. A ter cooling, the precipitated white crystals are suctioll-filtered off,, 3.7 g; Mp~ 209 211Cg ~ ~ .
2-Hexyl 2,7,7,9,9-pentamethyl1-o~a-3-o~co~4,8~diazaspiro[4 9 5]deca~e Preparation analogous to ~xample 37, with 2.84 g (0.01 mole) o~ stearic acid. 5.0 g o~ white cr~stals are obtained. Mpo 130 to 131C.
, ~amPle ~9 2-~e~yl-2,7,7,9,9-pentameth~l-1-oxa-3-oxo-4,8-diaza~piro[4,5]decane suocinate ' Procedure as in E~ample 37, with 6~20 ~ (ODO2 mole) of the .~
compound o~ ~xample 24 a~d 1.18 g (0~01 mole) o~ ~uccinic acid.
23 2-propyl-2,7,7, a~ a X7 ethanol 212 9,9-pentamethyl 3 3 -l-oxa-3-o~o-4, 8-diaza~piro[4, 5]decane.
24 2-hex~1 2,7,7, CH3 C6H~3 ethanol 191-192 9,9-pentameth~l -1 -sxa-3-oxo-4, 8~diazaspiro[4~5]
-decane.
2-hsptyl-2,7,7, C~ C H eth~l 187-188 ~g-pe~ta~ethyl-1 3 7 15 acetate o~a-2-o~o-4,8-diazaspiro[4,5~-decane, 26 2-undecyl-2~7,7,CH3 C11 23 ethyl 166 9,9-pentamethyl- aoetate 1-o~a-2-c~o-4,8~
:~ dia~aæp~ roE4 ~ 5]~
.~ decane.
; 27 2-~thyl-2 butyl- a H c~ ~9 ethyl 213 7,7,9,9~tetra- 2 5 4 acetate ~ methyl-1-oxa-2- .
: oxo-4 ~diaza-~piro~4,5]decan~, . :
~ 2B 2-ethyl~2-pentylC2~ C H1 eth~l 198-199 :. .
: -7,7,9,9~tetra- 5 5 1 acetate methyl-1-o~a-2-oxo-4 8-diaza~
.; 8 piro~4,5~decane.
29 2~2-diprop~1-7,7,3 7 3 7 ethanol 242-243 9,9-tetramethyl- .
1-oxa-2-oxo-4,8-diazaspiro[4~5]-: decane.
2~2-dibutyl-7,7,C4H9 C4H9 ethyl 225 .~ 9~9-tetramethyl- acetate 1~oxa-3-o~o-4,8-:. '.' diazaspiro[4,5]-. . decane~
__ ~ ,. ., , - 20 _ - , .-. . : , -.
, ~ . . .
~ .
, . .: , , ~1~233 .
2~2,474 Tetramethyl-7-oxa 20-oxo-3,21-diazaspiro~5,1,1172]heneioosane 45~5 g (0.3 mole) o~ triacetone-amine and 68~1 g (0.3 mole) of l-hydroxycyclodod~oane carbo~amide are lntroduced into 300 g o~
glacial acetic acid~ 62.7 g t0.64 mole) of concentrated H2~04 are added while stirring9 Stirring is continued ~or 15 hours at 70C and a~ter cooling the reaction ml~ture, the sul~uric ac~d salt of the desired compound is ~uctio~-filtered of~ Yield: 81 g = 59 ~ o~ the theoretical yield. ~he salt is dissolved in ethanol/water with heating, the solu~ion i8 stirred into concentrated aqueou~ a~monia, tha precipi-tated amine base i~ cuction~filtered off and rec~ystallized from cyclohe~a~on~0 The crystals are ~a~hed wlth ether. Mp. 273Co ~2 ~15 2 9 7,7,9,9-Pe~tamethy~ oxa-3-oxo-4,8-diaza~8-o~Ylspiro[4~5]decane 5 g of the compou~d according to E~ample 1, 50 ml of methanol, 9 ml ~ 3 ~ ~22~ 002 g of ~a2SO~ and 0.2 g of ethylenedi~mine tetraacetic acid are heated ~or 48 hour~ at 60C. Concentratio~
in ~Q~e is carried out, not to drgne~s, 20 ml o~ water i8 added~
suction-filtering is e~fected ~ollowed by recrystallization ~rom acetone/heptane, 3.5 g of orange-colored c~y~tals are obtai~ed.
Mp. 170~1 72Co . - 21 -:
The following were produced analogously to E~ample ~2:
_, .. _ _ .__ : ~x~mple Starting product Produot Mp C
No. Compound according to crystal-E~ample lized ~rom . .
_~ ___ ; 33 2-hexyl-2 9 7,7,9, 24 ether 112-113 9-pentameth~
oxa-3-oxo-4,8-dia-za-8-oxylspiro-C4,5]decane : ~4 2,2-diethyl 7.719~ 5 heptane/ 128-130 9-tetramethyl-1- acetone oxa-3-oxo-4,8-di-aza-8-oxylspiro-:~ -~4,5]decane .
~_ _ ___ '''' '''' : .. , . ~
2,2,7g7,8,9,9-heptsmethyl-1-ox~ 3-o~o~4,8-diazaspiro[4~5]deoane ::~
, ~5 24~0 g of the compound a¢cording to ~ample 21 are introduced into 256 g o~ 90 % ~o~mlc acidO i62 g of 37 ck formaldeh~de 801ution are added dropwise over a period o~ one hour, while stirring, at 20 to ~0C~ ~he mi~ture is heated slowlg to reflux and boiled until C2 evolution is complete (appro~i stely 15 hvurs). The formic acid is then distilled off a~d, after cooling, the residue is stirred into concentrated aqueous smmo~ia~ 15 ~ of white crystals having a melting point of 205 to 207C are precipitated~ -., '~' ,, ~' . , ".
, , , . :, .
~2~3 ~
2-Isobutyl~2,7,7,~,9,9-hexamethyl-1~oxa-3-oxospiro[4,5]decane ~his compound was obtained as in the above Example from 28~2 g of the product of Example 4~ Mp. 138C.
:
~k~Y~
2-He~yl 2,7,7,9,9-pentamethyl 1-oxa-3 oxo-4,8-dia~aspiro~4~5]decane p-ter~utylbenzoate 3.10 g (0.01 mole) of the compound according to Example 24 ~nd 1.78 g (0.01 mole) o~ p-tert~ butylbenzoio aoid are heated ~or 15 10 minutes in 20 ml of methanol. A ter cooling, the precipitated white crystals are suctioll-filtered off,, 3.7 g; Mp~ 209 211Cg ~ ~ .
2-Hexyl 2,7,7,9,9-pentamethyl1-o~a-3-o~co~4,8~diazaspiro[4 9 5]deca~e Preparation analogous to ~xample 37, with 2.84 g (0.01 mole) o~ stearic acid. 5.0 g o~ white cr~stals are obtained. Mpo 130 to 131C.
, ~amPle ~9 2-~e~yl-2,7,7,9,9-pentameth~l-1-oxa-3-oxo-4,8-diaza~piro[4,5]decane suocinate ' Procedure as in E~ample 37, with 6~20 ~ (ODO2 mole) of the .~
compound o~ ~xample 24 a~d 1.18 g (0~01 mole) o~ ~uccinic acid.
6,8 gram~ o~ white crystals having a melting point of 21~-214C.
,: , "~ ' '',, "'~ :"'','~. '~`, 33~i ~a~5 j Thi~ ~xample shows the light-stabillzing action o~ the com-pounds according to the invention when using in a poly-a-ola~in.
100 parts by wei~ht of pol~propylene havin~ a melt inde~
i5 of approximately 6g/10 min (determined a¢cording to AS~M D
1238-62 T ~ and a densit~ of 0.96 were mixed with : 0.10 parts by weight of pentaerythrityltetrakis[3-(3,5-ditert. -butyl-4-hydro~:~phe~yl ) -pro-pionate~ -1o 0.20 parts by weight o~ calcium stearate and O.30 parts by weight of one o~ the compounds according to the inve~tion, and the mi~ture ~as homogenized ~or 5 minute~ at 200C on a t~o- ~ -roller de~iceO ~he plastics melt was then compre~sed 200C ~to -:~
-~15 a plate 1 mm thiek. ~est bodie~ were stamped out o~ the cooled .` plate in accordanee with DIN 53 455. The test bodies required as .
-~ comparison samplea were produced analo~ou~ly but with the omission o~ the 3tabilizer to be tested. :
~o determine the light atabilitg the sa~ples were 3ubjected `~20 to rad~ation with alternati~g light in a Xenotest-~50-appar~tu~
of the ~irm Origi~al Hanau Quarzlampen Bm~H. The radiation inten-; sit~ wa~ modula~ed bg 6 IR ~i~dow~ and 1 ~V window (DI~ 53 387).
The expo~ure time waæ measured in hour~ ervice li~e), a~ter which the absolute elongation at break had reduced to 10 qcO ~he elongation at brsak was determined on a tensile testing machine o~
the firm Instron at a draw-o~ ~peed of` 5 om/min.
~he results are compiled in the following table:
, . . .
- 2~ -.' .
3~
Stabilizer of the in~rention Ser-rice life according to Example ( hours ) 4 < 1 000
,: , "~ ' '',, "'~ :"'','~. '~`, 33~i ~a~5 j Thi~ ~xample shows the light-stabillzing action o~ the com-pounds according to the invention when using in a poly-a-ola~in.
100 parts by wei~ht of pol~propylene havin~ a melt inde~
i5 of approximately 6g/10 min (determined a¢cording to AS~M D
1238-62 T ~ and a densit~ of 0.96 were mixed with : 0.10 parts by weight of pentaerythrityltetrakis[3-(3,5-ditert. -butyl-4-hydro~:~phe~yl ) -pro-pionate~ -1o 0.20 parts by weight o~ calcium stearate and O.30 parts by weight of one o~ the compounds according to the inve~tion, and the mi~ture ~as homogenized ~or 5 minute~ at 200C on a t~o- ~ -roller de~iceO ~he plastics melt was then compre~sed 200C ~to -:~
-~15 a plate 1 mm thiek. ~est bodie~ were stamped out o~ the cooled .` plate in accordanee with DIN 53 455. The test bodies required as .
-~ comparison samplea were produced analo~ou~ly but with the omission o~ the 3tabilizer to be tested. :
~o determine the light atabilitg the sa~ples were 3ubjected `~20 to rad~ation with alternati~g light in a Xenotest-~50-appar~tu~
of the ~irm Origi~al Hanau Quarzlampen Bm~H. The radiation inten-; sit~ wa~ modula~ed bg 6 IR ~i~dow~ and 1 ~V window (DI~ 53 387).
The expo~ure time waæ measured in hour~ ervice li~e), a~ter which the absolute elongation at break had reduced to 10 qcO ~he elongation at brsak was determined on a tensile testing machine o~
the firm Instron at a draw-o~ ~peed of` 5 om/min.
~he results are compiled in the following table:
, . . .
- 2~ -.' .
3~
Stabilizer of the in~rention Ser-rice life according to Example ( hours ) 4 < 1 000
7 < 1 00 9 < 1 000 ' C1 000 21 ~1 000 wi~hout (compari~on) 550 :, ':
~ ':
,.,~ ~.
~ .
~;
; ~ :
.
.
~ ':
,.,~ ~.
~ .
~;
; ~ :
.
.
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the general formula I
wherein R1 and R2 represent methyl groups, R3 and R4 are the same or different and represent hydrogen atoms, alkyl radicals or isoalkyl radicals having 1 to 30 carbon atoms, or represent aryl radicals having 6 or 10 carbon atoms, or R3 and R4 together with the carbon atoms to which they are bonded, form a cycloalkyl group having 4 to 20 carbon atoms, R5 represents a hydrogen atom, an oxygen atom, a hydroxy or an alkyl group having 1 to 4 carbon atoms, and HX represents a non-oxidizing mineral acid, an aliphatic or aromatic sulfonic or phosphonic acid, an aliphatic mono , di-or polycarboxylic acid or an aromatic mono- or di-carboxylic acid and m = 0 or 1 but when = N-R5 does not have a basic reaction, is always 0.
wherein R1 and R2 represent methyl groups, R3 and R4 are the same or different and represent hydrogen atoms, alkyl radicals or isoalkyl radicals having 1 to 30 carbon atoms, or represent aryl radicals having 6 or 10 carbon atoms, or R3 and R4 together with the carbon atoms to which they are bonded, form a cycloalkyl group having 4 to 20 carbon atoms, R5 represents a hydrogen atom, an oxygen atom, a hydroxy or an alkyl group having 1 to 4 carbon atoms, and HX represents a non-oxidizing mineral acid, an aliphatic or aromatic sulfonic or phosphonic acid, an aliphatic mono , di-or polycarboxylic acid or an aromatic mono- or di-carboxylic acid and m = 0 or 1 but when = N-R5 does not have a basic reaction, is always 0.
2. A compound as claimed in claim 1 in which R1 and R2 are methyl groups, R5 represents hydrogen and m represents 0.
3. A compound as claimed in claim 2. in which R3 is hydrogen and R4 is methyl, ethyl, propyl, butyl, isobutyl, pentyl, 2-ethylpropyl, 2-ethylpentyl and phenyl.
4. A compound as claimed in claim 2 in which R3 is a methyl group and R4 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, nonyl and undecyl.
5. A compound as claimed in claim 2 in which R3 is ethyl and R4 is butyl, pentyl and isopentyl.
6. A compound as claimed in claim 2 in which R3 and R4 are the same and represent methyl, ethyl, propyl, butyl, and pentyl.
7. A compound as claimed in claim 2 in which R3 and R4, together with the carbon atom to which they are bonded, represent a cyclopentyl, cyclohexyl or cyclododecyl ring. 27
8. A process for the preparation of a compound of the general formula I as defined in claim l in which a 2,2-dimethyl-6,6-dialkylpiperidone of the formula or the salt of such a piperidone is reacted with an equimolar amount of an .alpha.-hydroxyamide of the formula wherein R1, R2, R3 and R4 are as defined in claim 1, in an organic solvent, at a temperature in the range of 20 to 180°C
in the presence of a water-removing agent, wherein the reaction product obtained may be alkylated with an alkyl bromide having 1 to 4 carbon atoms or methylated with a mixture of formic acid and formaldehyde, CO2 being split off, or oxidized with H2O2.
in the presence of a water-removing agent, wherein the reaction product obtained may be alkylated with an alkyl bromide having 1 to 4 carbon atoms or methylated with a mixture of formic acid and formaldehyde, CO2 being split off, or oxidized with H2O2.
9. A process for stabilizing halogen-free, aliphatic .alpha.-olefin homo- and co-polymers and chlorine-containing vinyl homo- and co-polymers against the damaging influence of light, in which 0.01 to 5 parts by weight, based on the polymer, of a compound as claimed in claim 1 is added to the polymer.
10. A process as claimed in claim 9 in which at least one additional stabilizer is added to the polymer.
11. A synthetic organic polymer, stabilized against UV de-composition,containing 0.01 to 5 parts by weight, calculated on the polymer, of a stabilizer as claimed in claim 1.
12. A synthetic organic polymer as claimed in claim 11 in which the polymer is selected from the group of polyolefins, poly-vinyl chloride, polyvinyl acetate, polyacetals, polyesters, polyamides, polyacrylates, polyurethanes and epoxy resins.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2634957A DE2634957C3 (en) | 1976-08-04 | 1976-08-04 | l-Oxa-4,8-diaza-spiro- [43] -decanes, their preparation and their use as light stabilizers |
| DEP2634957.5 | 1976-08-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1102335A true CA1102335A (en) | 1981-06-02 |
Family
ID=5984665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA284,017A Expired CA1102335A (en) | 1976-08-04 | 1977-08-03 | 1-oxa-4,8-diazaspiro[4,5]decanes, their production and their use as agents for protection against light |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5318582A (en) |
| AT (1) | AT355314B (en) |
| AU (1) | AU508977B2 (en) |
| BE (1) | BE857477A (en) |
| BR (1) | BR7705123A (en) |
| CA (1) | CA1102335A (en) |
| DE (1) | DE2634957C3 (en) |
| DK (1) | DK348077A (en) |
| FR (1) | FR2360596A1 (en) |
| GB (1) | GB1563747A (en) |
| IE (1) | IE45327B1 (en) |
| IT (1) | IT1115382B (en) |
| LU (1) | LU77913A1 (en) |
| NL (1) | NL187074C (en) |
| ZA (1) | ZA774689B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2545292C3 (en) * | 1975-10-09 | 1980-05-29 | Hoechst Ag, 6000 Frankfurt | Azaadamantane compounds as stabilizers for organic polymer compositions |
| DE2738340A1 (en) * | 1977-08-25 | 1979-03-01 | Hoechst Ag | NEW UREA DERIVATIVES, THEIR PRODUCTION AND USE AS LIGHT PROTECTION AGENTS |
| DE2834962A1 (en) * | 1978-08-10 | 1980-02-21 | Hoechst Ag | METHOD FOR PRODUCING AZASPIRODECANES |
| EP0017617A3 (en) * | 1979-03-27 | 1980-10-29 | Ciba-Geigy Ag | Polyalkylpiperidine spirooxazolones, their application as light stabilisers and polymers stabilised therewith |
| DE2933732A1 (en) * | 1979-08-21 | 1981-03-26 | Hoechst Ag, 65929 Frankfurt | ALKYLATED DIAZASPIRODECANE, THEIR PRODUCTION AND USE AS A LIGHT PROTECTION AGENT |
| CH648036A5 (en) * | 1980-12-24 | 1985-02-28 | Sandoz Ag | 1-OXA-3,8-DIAZA-4-OXO-SPIRO (4,5) -DECAN COMPOUNDS. |
| DE3233954A1 (en) * | 1982-09-14 | 1984-03-15 | Chemische Werke Hüls AG, 4370 Marl | NEW SQUARE ACID AMIDE DERIVATIVES, THEIR USE AS STABILIZING AGENTS AND THE PLASTICS TREATED WITH THESE |
| DE3541664A1 (en) * | 1985-11-26 | 1987-06-11 | Hoechst Ag | OLIGOMERS DIAZASPIRODECANE, THEIR PRODUCTION AND THEIR USE AS LIGHT PROTECTION AGENTS FOR POLYMERS |
| JPH0513925Y2 (en) * | 1986-11-25 | 1993-04-14 | ||
| JP2002371046A (en) * | 2001-06-11 | 2002-12-26 | Showa Denko Kk | Method for producing 2-hydroxycarboxylic amide |
| EP2440557B1 (en) * | 2009-06-08 | 2017-04-05 | Basf Se | Novel sterically hindered amine light stabilizers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3431233A (en) * | 1965-11-26 | 1969-03-04 | Sankyo Co | Novel piperidine n-oxide polyolefin stabilizers |
| CA975365A (en) * | 1971-06-05 | 1975-09-30 | Eiko Mori | Piperidine derivatives and their use as stabilizers |
-
1976
- 1976-08-04 DE DE2634957A patent/DE2634957C3/en not_active Expired
-
1977
- 1977-07-29 NL NLAANVRAGE7708439,A patent/NL187074C/en not_active IP Right Cessation
- 1977-08-02 GB GB32339/77A patent/GB1563747A/en not_active Expired
- 1977-08-02 IT IT26426/77A patent/IT1115382B/en active
- 1977-08-03 JP JP9259577A patent/JPS5318582A/en active Granted
- 1977-08-03 AT AT571877A patent/AT355314B/en not_active IP Right Cessation
- 1977-08-03 DK DK348077A patent/DK348077A/en not_active Application Discontinuation
- 1977-08-03 ZA ZA00774689A patent/ZA774689B/en unknown
- 1977-08-03 IE IE1615/77A patent/IE45327B1/en unknown
- 1977-08-03 CA CA284,017A patent/CA1102335A/en not_active Expired
- 1977-08-03 BR BR7705123A patent/BR7705123A/en unknown
- 1977-08-03 AU AU27593/77A patent/AU508977B2/en not_active Expired
- 1977-08-03 LU LU77913A patent/LU77913A1/xx unknown
- 1977-08-04 FR FR7724058A patent/FR2360596A1/en active Granted
- 1977-08-04 BE BE179907A patent/BE857477A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AT355314B (en) | 1980-02-25 |
| AU508977B2 (en) | 1980-04-17 |
| AU2759377A (en) | 1979-02-08 |
| IE45327L (en) | 1978-02-04 |
| DK348077A (en) | 1978-02-05 |
| JPS5318582A (en) | 1978-02-20 |
| JPS6112913B2 (en) | 1986-04-10 |
| NL7708439A (en) | 1978-02-07 |
| FR2360596B1 (en) | 1982-07-30 |
| ATA571877A (en) | 1979-07-15 |
| NL187074B (en) | 1990-12-17 |
| ZA774689B (en) | 1978-07-26 |
| GB1563747A (en) | 1980-03-26 |
| IT1115382B (en) | 1986-02-03 |
| IE45327B1 (en) | 1982-07-28 |
| DE2634957B2 (en) | 1980-02-07 |
| DE2634957C3 (en) | 1980-10-02 |
| BR7705123A (en) | 1978-04-04 |
| FR2360596A1 (en) | 1978-03-03 |
| DE2634957A1 (en) | 1978-02-09 |
| LU77913A1 (en) | 1978-02-13 |
| BE857477A (en) | 1978-02-06 |
| NL187074C (en) | 1991-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1102335A (en) | 1-oxa-4,8-diazaspiro[4,5]decanes, their production and their use as agents for protection against light | |
| TWI527820B (en) | Novel sterically hindered amine light stabilizers | |
| CA1084055A (en) | Derivatives of 1-oxa-3,8-diaza-spiro- 4,5 -decanes, their preparation and application as light stabilizers | |
| US4340534A (en) | Ethers based on polyalkyl-1-oxadiazaspirodecanes | |
| US3542729A (en) | Stabilization of synthetic polymers | |
| US4405735A (en) | Substituted diazaspirodecanes, their preparation and their use as stabilizers for organic polymers, and the polymers thus stabilized | |
| US5550242A (en) | Process for the preparation of polyalkyl-1-oxa-diazaspirodecane compounds | |
| US4107139A (en) | 1-Oxa-4,8-diazaspiro[4,5]decanes and polymers stabilized against UV light with these compounds | |
| US4097587A (en) | 1,3,8-Triazaspiro 4.5!decane-2,4-dione polymer stabilizers | |
| IL44629A (en) | Stabilization of synthetic polymers by means of certain 1-substituted piperidine derivatives | |
| US4131599A (en) | Stabilization of poly(mono-olefins) | |
| AU693838B2 (en) | Process for the preparation of polyalkyl-1-oxa- diazaspirodecane compounds | |
| US4316025A (en) | Piperidine compounds | |
| US3645965A (en) | Stabilization of synthetic polymers with imidazolidine compounds | |
| US4007158A (en) | Novel piperidine derivatives for the stabilization of synthetic polymers | |
| US4239891A (en) | Substituted piperidine hydroxamides, their preparation, and their use as light stabilizers | |
| KR100851177B1 (en) | Phenolfree stabilization of polyolefins | |
| EP0232224A2 (en) | Piperidine compounds | |
| CA1285949C (en) | Oligomeric diazaoxaspirodecanes, preparation thereof and use thereof as light stabilizers for polymers | |
| EP0705836A1 (en) | Polyalkylpiperidine compounds | |
| US4055536A (en) | 4,4'-Bipiperidylidene derivatives and their use as stabilizers | |
| EP0062322A1 (en) | Improved process for synthesis of hindered amine stabilizers for polymeric materials | |
| US4142047A (en) | Substituted triazaadmantane compounds | |
| US3898303A (en) | Piperidine-spiro-hydantoin derivatives and their use as stabilizers | |
| US3884912A (en) | 4-Piperidone derivatives, their preparation and their use as stabilizers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |