Note: Descriptions are shown in the official language in which they were submitted.
~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~
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 _
~"
;
3S
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
'
,, '
... , ., . ~ ,
3S
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:
:
R3 R3 OH R3 OH
= 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 ;~
- 7 -
~,~J'
.
, .
, ~ .
,
2;~3~i
(IlX) R5 N~ R4
1/ 2 H O
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 _
~ ~ ,
,
.;
: ' . '
:~, . ' ' ,
315
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
- 11-
. ' :
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.
- 12 -
, , -
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
- 13 -
~,
' ' ' ' ' ',
.
,
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
- 14 -
.
., ," : , : ', '
.
,
.. . . .
.. . .
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
- 16 -
, ,.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:
, .
- 17 -
~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.
- 18 -
~' ~
~" .
',''
,'' ~ ~.
.' . - ', .''..
: ',
'
' ' . ' ' ' ' ' ' , .: ' '
,
~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 -
:
3S
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~ -
.,
'~' ,,
~'
- 22 -
. ,
".
,
,
,
. :, .
~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.
- 23 -
,: , "~ ' '',, "'~ :"'','~. '~`,
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
26
wi~hout (compari~on) 550
:, ':
~ ':
,.,~ ~.
~ .
~;
; ~ :
.
.
