CA1048529A - Antioxidant hindered phenolaldehydes - Google Patents
Antioxidant hindered phenolaldehydesInfo
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- CA1048529A CA1048529A CA74204919A CA204919A CA1048529A CA 1048529 A CA1048529 A CA 1048529A CA 74204919 A CA74204919 A CA 74204919A CA 204919 A CA204919 A CA 204919A CA 1048529 A CA1048529 A CA 1048529A
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/26—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups
- C07C47/27—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/28—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
- C07C47/36—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/38—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
- C07C47/46—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings containing hydroxy groups
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
New p-hydroxyphenyl aldehydes of the formula
New p-hydroxyphenyl aldehydes of the formula
Description
10485Z~
The invention relates to new phenolaldehydes, a process for their manufacture, their useforthe protection of substrates which are sensitive to oxidation and, as an industrial product, : :.
the substrates protected with their aid.
The new compounds correspond to the general formula I ~-R3 ~ H2 ~ ~ ~ CH-O
~.
in which Rl and ~ independently of one another denote hydro-gen or methyl, or Rl conjointly with R2 and/or R4 conjointly with ~ denotes tetramethylene, R2 denotes alkyl, cycloalkyl -: -or aralkyl, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl, cycloalkyl or aralkyl, R6 denotes alkyl, aralkyl, acyloxyalkyl, oxaalkyl or phenyl, R7 denotes alkyl, phenyl or the group R~
~3 - ~ - CH2 R
~ .
.
~)48529 in which Rl to ~ have the indicated meaning, or, conjointly with R6, denotes alkylene, and n denotes O or 1.
Preferred compounds are those of the formula I in which and R5 independently of one another denote hydrogen or methyl, or R conJointly with R2 and/or R4 conjointly with R5 denotes -.
tetramethylene, R2 denotes alkyl with 1 to 8 carbon atoms, ~ -cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl with. -1 to 8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl :-~
with 7-9 carbon atoms, R6 denotes alkyl with 1 to 8 carbon atoms, R7 denotes alkyl with 1 to 8 carbon atoms or the group R2 Rl R3--~--CH2 :~ , in which Rl to R~ have the indicated meaning, or, conjointly with R6, denotes alkylene with 2 to 11 carbon atoms, and n denotes O or 1.
Particular preference attaches to compounds of the formula I in which ~ and ~ independently of one another denote hydrogen or methyl, ~ denotes particularly hydrogen, R2 denotes alkyl with 1-4 carbon atoms or, conjointly with Rl, denote$
tetramethylene, R2 being preferably alkyl with 1 to 4 carbon atoms, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms or, conjointly with ~ , denotes tetramethylene, R4 being preferably alkyl with 1-4 carbon ato~s, R6 denotes alkyl with 1 to 4 carbon atoms or phenyl, R6 being preferably aIkyl with la4ss2s ~ ~
1-4 carbon atoms, R7 denotes alkyl with 1-4, preferably 1-2, carbon atoms or the group R2 Rl . . , R~ CHz R4 :- -in which Rl to ~ have the indicated meanIng, or, conjointly ~ ~-with R6, denotes alkylene with 4 or 5, pre~erably 5, carbon atoms, and n denotes 0 or 1, preferably 1.
m ose compounds of the formula I in which n denotes the number 1, are a special group, preferred because of their easy accessibility.
If, in formula I, R2, R3 and R4 denote alkyl, it can be methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, tert. butyl, n-amyl, sec.-amyl, tert.-amyl, hexyl, octyl or 1,1,3,3-tetramethylbutyl.
R2, R3 and R4 can denote a cycloalkyl group, such as, for example, cyclopentyl, cyclohexyl, a-methylcyclohexyl or cyclooctyl.
R2, R3, R4 and R6 can denote an aralkyl group, such as, for example, benzyl, a-phenylethyl or a,a-dLmethylbenzyl.
R6 meaning oxaalkyl, for example with 3 to 10 carbon atoms, can be 3-oxabutyl, 3-oxapentyl or 3-oxaheptyl.
If R6 denotes acyloxyalkyl with, for example, 4 to 20 carbon atoms, then "acyl" is the radical of an aliphatic or aromatic carboxylic acid with, for example, 2 to 18 carbon . : . .
1~4~529 atoms, such as an alkanoic acid such as acetic acid, propionic acid, caproic acid, lauric acid or stearic acid or an unsub-stituted or substituted benzoic acid, such as benzoic acid, ;
p-tert.butylbenzoic acid or p-tert.octylbenzoic acid. Acyl-oxy is, for example, 2-acetoxyethyl, 2-propionyloxyethyl,
The invention relates to new phenolaldehydes, a process for their manufacture, their useforthe protection of substrates which are sensitive to oxidation and, as an industrial product, : :.
the substrates protected with their aid.
The new compounds correspond to the general formula I ~-R3 ~ H2 ~ ~ ~ CH-O
~.
in which Rl and ~ independently of one another denote hydro-gen or methyl, or Rl conjointly with R2 and/or R4 conjointly with ~ denotes tetramethylene, R2 denotes alkyl, cycloalkyl -: -or aralkyl, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl, cycloalkyl or aralkyl, R6 denotes alkyl, aralkyl, acyloxyalkyl, oxaalkyl or phenyl, R7 denotes alkyl, phenyl or the group R~
~3 - ~ - CH2 R
~ .
.
~)48529 in which Rl to ~ have the indicated meaning, or, conjointly with R6, denotes alkylene, and n denotes O or 1.
Preferred compounds are those of the formula I in which and R5 independently of one another denote hydrogen or methyl, or R conJointly with R2 and/or R4 conjointly with R5 denotes -.
tetramethylene, R2 denotes alkyl with 1 to 8 carbon atoms, ~ -cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl with. -1 to 8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl :-~
with 7-9 carbon atoms, R6 denotes alkyl with 1 to 8 carbon atoms, R7 denotes alkyl with 1 to 8 carbon atoms or the group R2 Rl R3--~--CH2 :~ , in which Rl to R~ have the indicated meaning, or, conjointly with R6, denotes alkylene with 2 to 11 carbon atoms, and n denotes O or 1.
Particular preference attaches to compounds of the formula I in which ~ and ~ independently of one another denote hydrogen or methyl, ~ denotes particularly hydrogen, R2 denotes alkyl with 1-4 carbon atoms or, conjointly with Rl, denote$
tetramethylene, R2 being preferably alkyl with 1 to 4 carbon atoms, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms or, conjointly with ~ , denotes tetramethylene, R4 being preferably alkyl with 1-4 carbon ato~s, R6 denotes alkyl with 1 to 4 carbon atoms or phenyl, R6 being preferably aIkyl with la4ss2s ~ ~
1-4 carbon atoms, R7 denotes alkyl with 1-4, preferably 1-2, carbon atoms or the group R2 Rl . . , R~ CHz R4 :- -in which Rl to ~ have the indicated meanIng, or, conjointly ~ ~-with R6, denotes alkylene with 4 or 5, pre~erably 5, carbon atoms, and n denotes 0 or 1, preferably 1.
m ose compounds of the formula I in which n denotes the number 1, are a special group, preferred because of their easy accessibility.
If, in formula I, R2, R3 and R4 denote alkyl, it can be methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, tert. butyl, n-amyl, sec.-amyl, tert.-amyl, hexyl, octyl or 1,1,3,3-tetramethylbutyl.
R2, R3 and R4 can denote a cycloalkyl group, such as, for example, cyclopentyl, cyclohexyl, a-methylcyclohexyl or cyclooctyl.
R2, R3, R4 and R6 can denote an aralkyl group, such as, for example, benzyl, a-phenylethyl or a,a-dLmethylbenzyl.
R6 meaning oxaalkyl, for example with 3 to 10 carbon atoms, can be 3-oxabutyl, 3-oxapentyl or 3-oxaheptyl.
If R6 denotes acyloxyalkyl with, for example, 4 to 20 carbon atoms, then "acyl" is the radical of an aliphatic or aromatic carboxylic acid with, for example, 2 to 18 carbon . : . .
1~4~529 atoms, such as an alkanoic acid such as acetic acid, propionic acid, caproic acid, lauric acid or stearic acid or an unsub-stituted or substituted benzoic acid, such as benzoic acid, ;
p-tert.butylbenzoic acid or p-tert.octylbenzoic acid. Acyl-oxy is, for example, 2-acetoxyethyl, 2-propionyloxyethyl,
2-capryloxyethyl, 2-lauryloxyethyl, 2-stearyloxyethyl,
3-acetoxypropyl, 3-propionyloxypropyl, 3-lauryloxypropyl, 3-capryloxypropyl, 3-stearyloxypropyl or 3-benzoyloxypropyl.
If R6 and R7 in formulaI denote an alkyl group, it can be methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl or n-octyl.
If R6 and R7 conjointly denote an alkylene group, it can be ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene or undecamethylene.
Examples of compounds of the ~ormula I are: 3-(3-tert.butyl-4-hydroxy-5-methylphenyl)-2,2-dimethyi-propionaldehyde, 3-(3-tert.butyl-4-hydroxy-5,6-dimethylphenyl)-2,2-dimethyl-propionaldehyde, 3-(3,5-di-cyclooctyl-4-hydroxyphenyl)-2,2-dimethyl-propionaldehyde, 3-(4-hydroxy-3,5-di--methylcyclo-hexylphenyl)-2,2- dimethyl-propionaldehyde, 3-(4-hydroxy-3,5-di-~-phenylethyl-phenyl)-2,2-dimethyl-propionaldehyde, 2-ethyl-2-(3,5-di-butyl-4-hydroxybenzyl)-caproaldehyde, 2-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2-octyl-capraldehyde, 1-(3,5-di-tert.butyl-
If R6 and R7 in formulaI denote an alkyl group, it can be methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl or n-octyl.
If R6 and R7 conjointly denote an alkylene group, it can be ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene or undecamethylene.
Examples of compounds of the ~ormula I are: 3-(3-tert.butyl-4-hydroxy-5-methylphenyl)-2,2-dimethyi-propionaldehyde, 3-(3-tert.butyl-4-hydroxy-5,6-dimethylphenyl)-2,2-dimethyl-propionaldehyde, 3-(3,5-di-cyclooctyl-4-hydroxyphenyl)-2,2-dimethyl-propionaldehyde, 3-(4-hydroxy-3,5-di--methylcyclo-hexylphenyl)-2,2- dimethyl-propionaldehyde, 3-(4-hydroxy-3,5-di-~-phenylethyl-phenyl)-2,2-dimethyl-propionaldehyde, 2-ethyl-2-(3,5-di-butyl-4-hydroxybenzyl)-caproaldehyde, 2-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2-octyl-capraldehyde, 1-(3,5-di-tert.butyl-
4-hydroxybenzyl)-hexahydro-benzaldehyde, 1-(3-tert.butyl-4-hydroxy-5,6-di-methylbenzyl)-hexahydro-benzaldehyde, 1-(3-tert.butyl-4-hydroxy-5-methylbenzyl)-cyclooctane-carboxaldehyde, (3,5-di-tert.butyl-4-hydroxyphenyl)-acetaldehyde, (3-tert.butyl-4-hydroxy 5-methylphenyl)-aGetaldehyde, _4_ ~485Z9 -(3-tert.butyl-4-hydroxy-5,6-dimethylphenyl)-acetaldehyde, 2,2-bis-(3-tert butyl-4-hydroxy-5--a-methylbenzyl)-propionalde-hyde, 2,2-bis-(3,5-di-tert.butyl-4-hydroxybenzyl)-caprylaldehyde and 2,2-bis-(3,5-di-tert.butyl-4-hydroxybenzyl)oenanthaldehyde.
The compounds of the formula Ia according to the inven-tion 2 Rl R3 - ~ O ~ _ CH2-CH=O (Ia) X /~R ' ' ' 4 s : . :
that is to say compounds of the formula I in which n denotes 0, can be obtained in a manner which is in itself known from compounds of the formula II
R2~Rl .
R3 - ~ C~I2-CO-Cl (II) by reduction with hydrogen gas in the presence of specific catalyst systems (Rosenmund reduction).
The compounds of the formula Ib HO - ~ H2- C - CH=O (Ib) :. .
1~4~529 in which Rl denotes hydrogen, or, conjointly with R2, denotes tetramethylene, Rl being preferably hydrogen, R5 denotes hydrogen or methyl or, conjointly with R4, denotes tetramethyl-ene, R5 being preferably hydrogen or methyl, R2 and R4 independently of one another denote alkyl, cycloalkyl or aralkyl, and R6 and R7 independently of one another denote alkyl or conjointly denote alkylene, can be obtained in a further process which is in itself known by reacting compounds of the formula III
R' HO ~ CH2 _ X
. R
in which X denotes halogen such as chlorine or bromine, with.
compounds of the formula IV
H - C - CH=O (IV) I
in the presence of concentrated aqueous sodium hydroxide solu-tion and catalytic amounts of a tetraalkylammonium salt in a so-called "phase transfer catalyséd" reaction.
It has further been found that the compounds, which fall under formula I, of the formula Ic 1~)48S29 R2 Rl 6 :-~ ,.
~10 ~ CH2 1 :- CH==O ~ - (Ic) - .
R'J ~R 7 in which Rl denotes hydrogen or, conjointly with R2, denotes tetramethylene, Rl being preferably hydrogen, R5 denotes . -hydrogen or methyl or, conjointly with R4, denotes tetramethy~
lene, R5 being preferably hydrogen or methyl, R2 and RL
independently of one another denote alkyl, cycloalkyl or - -aralkyl, R6 denotes alkyl, and R7 denotes alkyl or the group ; , ~10~C~2- ~.,.' R4 ~5 m in which Rl, R2, RL and R5 have the indicated meaning, or, conjointly with R6, denotes alkylene, can be obtained, surprisingly, in a new process by reacting a compound of the ~-formuia V
HO - ~ CH2 -S - C- N R8 Rg (V) .
.. . . .
1~48S29 wherein Rl, R2, RL and ~ have the meaning defined in formula Ic and R8 and Rg independently of one another denote alkyl or conjointly, with the inclusion of the nitrogen atom, denote a saturated, heterocyclic 5- or 6-membered ring, with a compound of the formula ~I
R~
H - C - CH=O (VI) R~
wherein R6 denotes alkyl and R7 denotes hydrogen or alkyl or, conjointly with R6, denotes alkylene,in a solvent in the presence of a base.
In this reaction those compounds of the formula V are preferably employed in which R8 and Rg independently of one another denote alkyl with 1 to 5 carbon atoms or conjointly, with the inclusion of the nitrogen atom, denote the radical of morpholine or piperidine.
Compounds of the formula V in which R8 and Rg denote methyl or ethyl are particularly preferentially employed.
The process according to the invention is carried out in a solvent. Suitable solvents are alcohols such as methanol, ethanol, iso-propanol, sec.-butanol, tert.-butanol or amyl alcohol, aliphatic ethers such as dibutyl ether, tetrahydro-furane or dioxane, hydrocarbons such as hexane, heptane, octane, ligroin, decalin, cyclohexane, benzene, toluene or xylene, or aprotic polar solvents such as dimethylformamide, dimethyl acetamide or dimethylsulphoxide.
Examples of suitable bases in the process according to ~ . .. , ~ . . ~
i~485Z9 - ;
the invention are alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alcoholates, such as sodium ~ -methylate, sodium ethylate, magnesium ethylate, potassium ~-isopropylate or potassium tert.butylate, or hydrides, such as lithium hydride, sodium hydride or potassium hydride It has been shown that the process according to the invention can be carried out particularly advantageously in a -~ne-phase reaction mixture J for example in a solvent miscible with water, such as lower alcohols, for example methanol, ethanol or isopropanol, ethers, such as dioxane and tetrahydro-furane, or aprotic polar solvents, such as dimethylformamide or dimethylsulphoxide, using an aqueous or alcoholic or aqueous-alcoholic solution of the base, an alkali metal hydroxide or alkali metal alcoholate preferably being employed as the base.
Surprisingly, the aldehyde of the formula VI is not destroyed as a result of side reactions, as would have been expected on the basis of the literature. Instead, the com-pounds of-the formula Ic are obtained under these reaction ;
conditions in substantially better purity and higher yield than ;
would be the case in known processes.
In order to prepare compounds of the formula Ic in which R7 denotes alkyl or, conjointly with R6, denotes alkylene, the aldehyde of the formula VI wherein R7 denotes alkyl or, conjointly with R6, denotes alkylene, is advantageously used in a 5 - 40% strength excess over the compound of the formula V, the base being in an approximately molar ratio to this compound.
In order to prepare compounds of the formula Ic in which R7 denotes the group '" .
_g_ ~.
' ~ ' 1~48S29 the aldehyde of the formula VI in which R7 denotes hydrogen, is advantageously used in an approximately half-molar ratio to the compound o~ the formula V, the base being in an approximately molar ratio to the compound of the formula V.
The temperatures at which the process according to the invention is carried out are not critical and are, for example, between -10 and +120C. The reaction is preferably carried out at elevated temperature, for example at 40 - 80C.
The process according to the invention is preferably carried out under an atmosphere o~ nitrogen or rare gas. It is possible initially to take the base in the solvent and to add dropwise the compounds of the formulae V and VI, together or separately, optionally in a dissolved form. In the particu- i larly advantageous one-phase embodiment, it is advantageous initially to take the two compounds of the formulae V and VI
in the solvent and to add the base slowly dropwise, preferably ~:
at elevated temperature and dissolved in water or in an organic :
solvent.
In a simplified embodiment of the inventive processS
a compound of the formula VII
-i~4~529 ~2 Rl HO ~ (VII) R4 ~5 is initially taken, together with carbon disulphide and a formaldehyde donor, in the solvent, a secondary amine of the formula VIII
/ R8 , ~:
HN ~ (VIII) is added dropwise as such or in a solvent, and the reaction mixture is then warmed. A compound of the formula VI is added subsequently and the solution of a base is added dropwise. In this embodiment the compound of the formula Ic is obtained in a practically quantitative yield and high purity. One advan-tage of this embodiment consists of the fact that the desired compounds of the formula Ic are obtained starting directly from cheap starting products and without isolation of the intermediate product of the formula V.
In this simplified embodiment of the inventive process, formaldehyde in -the form of an aqueous solution can be employed as the formaldehyde donor. Preferably, however, paraformal-dehyde is employed. One of the water-miscible, organic solvents mentioned, preferably an alcohol such as isopropanol, is used as the solvent. An alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, or an alcoholate, such :., ., ~
. .
104~3S29 as sod.ium methylate, sodium ethylate or sodium isopropylate, is preferably employed as the base An aqueous alkali metal hydroxide solution is used particularly preferentially.
In the formulae VII and VIII, the substituents Rl, R2, R4, R5, R8 and Rg denote what is quoted under formula V. The starting products of the formulae II, III, IV, V, VI, VII and VIII are known or are easily accessible by generally known methods.
The compounds of the formula I are used as stabilisers, particul.arly processing stabilisers, for organic substrates.
They are also valuable intermediate products for the manufac-ture of stabilisers for organic substrates.
For example, by reacting the compounds of the formula I with alkali metal cyanide and ammonium carbonate, it is poss-ible to obtain stabilisers of the formula IX
~ ~ 2 ~I ~ H C~ ~
in which q is 1 to 3, n, Rl, R2, R3, R4, R5t R6 and R7 ha~e ~.
the same meanings as indicated in the formula I and Rlo repre- ;
sents, if q = 1, hydrogen or a substituted or unsubstituted alkyl, alkenyl or cycloalkyl group, if q = 2,.an alkylene group :~
which is optionally interrupted by ester functions, hetero-atoms :~.
and/or benzene rings, or, if q = 3, an alkanetriyl group or a ~ :
, , :: , - ~ . ~
~4~Z9 trifunctional group which contains a heterocyclic radical. -~
The following are examples of suitable substrates to ~ .
be stabilised by means of the compounds of the formula I
according to the invention or secondary products thereof of the formula IX:
1. Polymers which are derived from hydrocarbons with single or double unsaturation, such as polyolefines, such as, for example, polyethylene, which can optionally be crosslinked, polypropylene, polyisobutylene, polymethylbutene-l, poly- -methylpentene-l, polybutene-l, polyisoprene, polybutadiene, polystyrene, polyisobutylene, copolymers of the monomers on which the homopolymers mentioned are based, such as ethylene-propylene copolymers, propylene-butene-l copolymers, propylene-isobutylene copolymers, styrene-butadiene copolymers and terpolymers of ethylene and propylene with a diene, such as, for example, hexadiene, dicyclopentadiene or ethylidene-norbornene; mixtures of the abovementioned homopolymers, such as, for example, mixtures of polypropylene and polyethy].-ene, polypropylene and polybutene-l, or polypropylene and poly- -isobutylene.
2. Vinyl polymers containing halogen, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, but also polychloroprene and chlorinated rubbers 3. Polymers ~hich are derived from ~,~-unsaturated acids and their derivatives, such as polyacrylates and poly-methacrylates, polyacrylamides and polyacrylonitrile, as well as their copolymers with other vinyl compounds, such as acrylo-nitrile/butadiene/styrene, acrylonitrile/styrene and ~ :
.
104~
acrylonitrile/styrene/acrvlic ester copolymers.
4. Polymer-s which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as poly-vinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and their copolymers with other vinyl compounds, such as ethylene/vinyl acetate copolymers.
The compounds of the formula Ia according to the inven-tion 2 Rl R3 - ~ O ~ _ CH2-CH=O (Ia) X /~R ' ' ' 4 s : . :
that is to say compounds of the formula I in which n denotes 0, can be obtained in a manner which is in itself known from compounds of the formula II
R2~Rl .
R3 - ~ C~I2-CO-Cl (II) by reduction with hydrogen gas in the presence of specific catalyst systems (Rosenmund reduction).
The compounds of the formula Ib HO - ~ H2- C - CH=O (Ib) :. .
1~4~529 in which Rl denotes hydrogen, or, conjointly with R2, denotes tetramethylene, Rl being preferably hydrogen, R5 denotes hydrogen or methyl or, conjointly with R4, denotes tetramethyl-ene, R5 being preferably hydrogen or methyl, R2 and R4 independently of one another denote alkyl, cycloalkyl or aralkyl, and R6 and R7 independently of one another denote alkyl or conjointly denote alkylene, can be obtained in a further process which is in itself known by reacting compounds of the formula III
R' HO ~ CH2 _ X
. R
in which X denotes halogen such as chlorine or bromine, with.
compounds of the formula IV
H - C - CH=O (IV) I
in the presence of concentrated aqueous sodium hydroxide solu-tion and catalytic amounts of a tetraalkylammonium salt in a so-called "phase transfer catalyséd" reaction.
It has further been found that the compounds, which fall under formula I, of the formula Ic 1~)48S29 R2 Rl 6 :-~ ,.
~10 ~ CH2 1 :- CH==O ~ - (Ic) - .
R'J ~R 7 in which Rl denotes hydrogen or, conjointly with R2, denotes tetramethylene, Rl being preferably hydrogen, R5 denotes . -hydrogen or methyl or, conjointly with R4, denotes tetramethy~
lene, R5 being preferably hydrogen or methyl, R2 and RL
independently of one another denote alkyl, cycloalkyl or - -aralkyl, R6 denotes alkyl, and R7 denotes alkyl or the group ; , ~10~C~2- ~.,.' R4 ~5 m in which Rl, R2, RL and R5 have the indicated meaning, or, conjointly with R6, denotes alkylene, can be obtained, surprisingly, in a new process by reacting a compound of the ~-formuia V
HO - ~ CH2 -S - C- N R8 Rg (V) .
.. . . .
1~48S29 wherein Rl, R2, RL and ~ have the meaning defined in formula Ic and R8 and Rg independently of one another denote alkyl or conjointly, with the inclusion of the nitrogen atom, denote a saturated, heterocyclic 5- or 6-membered ring, with a compound of the formula ~I
R~
H - C - CH=O (VI) R~
wherein R6 denotes alkyl and R7 denotes hydrogen or alkyl or, conjointly with R6, denotes alkylene,in a solvent in the presence of a base.
In this reaction those compounds of the formula V are preferably employed in which R8 and Rg independently of one another denote alkyl with 1 to 5 carbon atoms or conjointly, with the inclusion of the nitrogen atom, denote the radical of morpholine or piperidine.
Compounds of the formula V in which R8 and Rg denote methyl or ethyl are particularly preferentially employed.
The process according to the invention is carried out in a solvent. Suitable solvents are alcohols such as methanol, ethanol, iso-propanol, sec.-butanol, tert.-butanol or amyl alcohol, aliphatic ethers such as dibutyl ether, tetrahydro-furane or dioxane, hydrocarbons such as hexane, heptane, octane, ligroin, decalin, cyclohexane, benzene, toluene or xylene, or aprotic polar solvents such as dimethylformamide, dimethyl acetamide or dimethylsulphoxide.
Examples of suitable bases in the process according to ~ . .. , ~ . . ~
i~485Z9 - ;
the invention are alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alcoholates, such as sodium ~ -methylate, sodium ethylate, magnesium ethylate, potassium ~-isopropylate or potassium tert.butylate, or hydrides, such as lithium hydride, sodium hydride or potassium hydride It has been shown that the process according to the invention can be carried out particularly advantageously in a -~ne-phase reaction mixture J for example in a solvent miscible with water, such as lower alcohols, for example methanol, ethanol or isopropanol, ethers, such as dioxane and tetrahydro-furane, or aprotic polar solvents, such as dimethylformamide or dimethylsulphoxide, using an aqueous or alcoholic or aqueous-alcoholic solution of the base, an alkali metal hydroxide or alkali metal alcoholate preferably being employed as the base.
Surprisingly, the aldehyde of the formula VI is not destroyed as a result of side reactions, as would have been expected on the basis of the literature. Instead, the com-pounds of-the formula Ic are obtained under these reaction ;
conditions in substantially better purity and higher yield than ;
would be the case in known processes.
In order to prepare compounds of the formula Ic in which R7 denotes alkyl or, conjointly with R6, denotes alkylene, the aldehyde of the formula VI wherein R7 denotes alkyl or, conjointly with R6, denotes alkylene, is advantageously used in a 5 - 40% strength excess over the compound of the formula V, the base being in an approximately molar ratio to this compound.
In order to prepare compounds of the formula Ic in which R7 denotes the group '" .
_g_ ~.
' ~ ' 1~48S29 the aldehyde of the formula VI in which R7 denotes hydrogen, is advantageously used in an approximately half-molar ratio to the compound o~ the formula V, the base being in an approximately molar ratio to the compound of the formula V.
The temperatures at which the process according to the invention is carried out are not critical and are, for example, between -10 and +120C. The reaction is preferably carried out at elevated temperature, for example at 40 - 80C.
The process according to the invention is preferably carried out under an atmosphere o~ nitrogen or rare gas. It is possible initially to take the base in the solvent and to add dropwise the compounds of the formulae V and VI, together or separately, optionally in a dissolved form. In the particu- i larly advantageous one-phase embodiment, it is advantageous initially to take the two compounds of the formulae V and VI
in the solvent and to add the base slowly dropwise, preferably ~:
at elevated temperature and dissolved in water or in an organic :
solvent.
In a simplified embodiment of the inventive processS
a compound of the formula VII
-i~4~529 ~2 Rl HO ~ (VII) R4 ~5 is initially taken, together with carbon disulphide and a formaldehyde donor, in the solvent, a secondary amine of the formula VIII
/ R8 , ~:
HN ~ (VIII) is added dropwise as such or in a solvent, and the reaction mixture is then warmed. A compound of the formula VI is added subsequently and the solution of a base is added dropwise. In this embodiment the compound of the formula Ic is obtained in a practically quantitative yield and high purity. One advan-tage of this embodiment consists of the fact that the desired compounds of the formula Ic are obtained starting directly from cheap starting products and without isolation of the intermediate product of the formula V.
In this simplified embodiment of the inventive process, formaldehyde in -the form of an aqueous solution can be employed as the formaldehyde donor. Preferably, however, paraformal-dehyde is employed. One of the water-miscible, organic solvents mentioned, preferably an alcohol such as isopropanol, is used as the solvent. An alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, or an alcoholate, such :., ., ~
. .
104~3S29 as sod.ium methylate, sodium ethylate or sodium isopropylate, is preferably employed as the base An aqueous alkali metal hydroxide solution is used particularly preferentially.
In the formulae VII and VIII, the substituents Rl, R2, R4, R5, R8 and Rg denote what is quoted under formula V. The starting products of the formulae II, III, IV, V, VI, VII and VIII are known or are easily accessible by generally known methods.
The compounds of the formula I are used as stabilisers, particul.arly processing stabilisers, for organic substrates.
They are also valuable intermediate products for the manufac-ture of stabilisers for organic substrates.
For example, by reacting the compounds of the formula I with alkali metal cyanide and ammonium carbonate, it is poss-ible to obtain stabilisers of the formula IX
~ ~ 2 ~I ~ H C~ ~
in which q is 1 to 3, n, Rl, R2, R3, R4, R5t R6 and R7 ha~e ~.
the same meanings as indicated in the formula I and Rlo repre- ;
sents, if q = 1, hydrogen or a substituted or unsubstituted alkyl, alkenyl or cycloalkyl group, if q = 2,.an alkylene group :~
which is optionally interrupted by ester functions, hetero-atoms :~.
and/or benzene rings, or, if q = 3, an alkanetriyl group or a ~ :
, , :: , - ~ . ~
~4~Z9 trifunctional group which contains a heterocyclic radical. -~
The following are examples of suitable substrates to ~ .
be stabilised by means of the compounds of the formula I
according to the invention or secondary products thereof of the formula IX:
1. Polymers which are derived from hydrocarbons with single or double unsaturation, such as polyolefines, such as, for example, polyethylene, which can optionally be crosslinked, polypropylene, polyisobutylene, polymethylbutene-l, poly- -methylpentene-l, polybutene-l, polyisoprene, polybutadiene, polystyrene, polyisobutylene, copolymers of the monomers on which the homopolymers mentioned are based, such as ethylene-propylene copolymers, propylene-butene-l copolymers, propylene-isobutylene copolymers, styrene-butadiene copolymers and terpolymers of ethylene and propylene with a diene, such as, for example, hexadiene, dicyclopentadiene or ethylidene-norbornene; mixtures of the abovementioned homopolymers, such as, for example, mixtures of polypropylene and polyethy].-ene, polypropylene and polybutene-l, or polypropylene and poly- -isobutylene.
2. Vinyl polymers containing halogen, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, but also polychloroprene and chlorinated rubbers 3. Polymers ~hich are derived from ~,~-unsaturated acids and their derivatives, such as polyacrylates and poly-methacrylates, polyacrylamides and polyacrylonitrile, as well as their copolymers with other vinyl compounds, such as acrylo-nitrile/butadiene/styrene, acrylonitrile/styrene and ~ :
.
104~
acrylonitrile/styrene/acrvlic ester copolymers.
4. Polymer-s which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as poly-vinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and their copolymers with other vinyl compounds, such as ethylene/vinyl acetate copolymers.
5. Homopolymers and copolymers which are derived from epoxides, such as polyethylene oxide or the polymers which are derived from bis-glycidyl ethers.
6. Polyacetals, such as polyoxymethylene and polyoxy-ethylene, as well as those polyoxymethylenes which contain ethylene oxide as the comonomer.
7. Polyphenylene oxides.
8. Polyurethanes and polyureas.
9. Polycarbonates.
10. Polysulphones.
11. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6, poly-amide 6/6, polyamide 6/10, polyamide 11 and polyamide 12.
12. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones 9 such as polyethylene glycol terephtha-late or poly-1,4-dimethylol-cyclohexane terephthalate.
13. Crosslinked polymers which are derived from aldehydes on the one hand and phenols, ureas and melamines on the other, such as phenol-formaldehyde~ urea-formaldehyde
-14-. . . ~ . ~ , , . . ~ -1~48S29 ~ ~
and melamine-formaldehyde resins ;
14. Alkyd resins, such as glycerine-phthalic acid resins and their mixtures with melamine-formaldehyde resins.
Unsa-turated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, with vinyl compounds as crosslinking agents, and also their halogen-containing modifications of low inflammability.
16. Natural polymers such as cellulose, rubber, proteins and their polymer-homologously chemically modified derivatives, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the celluIose ethers, such as methylcellulose.
17. Natural and synthetic organic substances which are pure monomeric compounds or mixtures of such, for example mineral oils, animal and vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters and mixtures of synthetic esters with mineral oils in any desired weight ratios.
The compounds of the formula I are incorporated in the substrates in a concentration of 0.005 to 5% by weight, rela-tive to -the material to be s-tabilised.
Preferably, 0.01 to 1.0, particularly preferably 0.02 to 0.5, % by weight of the compounds, relative to the material to be stabilised, are incorporated into the latter. The incorporation can be carried out, for example, by mixing in at least one of the compounds of the formula I and optionally further additives by the methods customary in the art, before or during shaping, or by applying the compounds, dissolved or dispersed, to the polymer, where appropriate with subsequent
and melamine-formaldehyde resins ;
14. Alkyd resins, such as glycerine-phthalic acid resins and their mixtures with melamine-formaldehyde resins.
Unsa-turated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, with vinyl compounds as crosslinking agents, and also their halogen-containing modifications of low inflammability.
16. Natural polymers such as cellulose, rubber, proteins and their polymer-homologously chemically modified derivatives, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the celluIose ethers, such as methylcellulose.
17. Natural and synthetic organic substances which are pure monomeric compounds or mixtures of such, for example mineral oils, animal and vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters and mixtures of synthetic esters with mineral oils in any desired weight ratios.
The compounds of the formula I are incorporated in the substrates in a concentration of 0.005 to 5% by weight, rela-tive to -the material to be s-tabilised.
Preferably, 0.01 to 1.0, particularly preferably 0.02 to 0.5, % by weight of the compounds, relative to the material to be stabilised, are incorporated into the latter. The incorporation can be carried out, for example, by mixing in at least one of the compounds of the formula I and optionally further additives by the methods customary in the art, before or during shaping, or by applying the compounds, dissolved or dispersed, to the polymer, where appropriate with subsequent
-15-evaporation of the solvent.
In -the case o~ crosslinked polyethylene~ the compounds are added before the crosslinking.
The compounds of the formula I can also be added before or during the polymerisation, it being possible, by a potential incorporation into the polymer chain, to obtain stabilised substrates in which the stabilisèrs are not volatile or sucep-tible to extraction.
me ~ollowing may be mentioned as examples of further additives with which the stabilisers can be conjointly employed:
1 Antioxidants ~
1.1 SimPle 2.6-dialkylphenols, such as, ~or example, 2,6-di- ;
- ;.
tert.-butyl-4-methylphenol, 2-tert -butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-dioctadecyl-4-methylphenol.
1.2 Derivatives of alkylated hydroquinones, such as, for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amyl-hydroquinone, 2,6-di-tert.-butyl-hydroquinone, 2,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, tris-(3,5-di-tert.-butyl-4-hydroxyphenyl)phosphite, 3,5-di-tert.-butyl-4-hydroxyphenylstearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)adipate.
1.3 Hydroxylated thiodiphenyl ethers, such as, for example, 2,2'-thio-bis-(6~tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4~4'-bis-(2,6-dimethyl-4-hydroxyphenyl)-disulphide.
In -the case o~ crosslinked polyethylene~ the compounds are added before the crosslinking.
The compounds of the formula I can also be added before or during the polymerisation, it being possible, by a potential incorporation into the polymer chain, to obtain stabilised substrates in which the stabilisèrs are not volatile or sucep-tible to extraction.
me ~ollowing may be mentioned as examples of further additives with which the stabilisers can be conjointly employed:
1 Antioxidants ~
1.1 SimPle 2.6-dialkylphenols, such as, ~or example, 2,6-di- ;
- ;.
tert.-butyl-4-methylphenol, 2-tert -butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-dioctadecyl-4-methylphenol.
1.2 Derivatives of alkylated hydroquinones, such as, for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amyl-hydroquinone, 2,6-di-tert.-butyl-hydroquinone, 2,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, tris-(3,5-di-tert.-butyl-4-hydroxyphenyl)phosphite, 3,5-di-tert.-butyl-4-hydroxyphenylstearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)adipate.
1.3 Hydroxylated thiodiphenyl ethers, such as, for example, 2,2'-thio-bis-(6~tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4~4'-bis-(2,6-dimethyl-4-hydroxyphenyl)-disulphide.
-16-' . .' ''' :.. , . ~, . - -1048~Z9 1.4 e_~Y _~L,~ LLDb~C~, such as, for example, 2,2'-methylene-bis-(6-tert.butyl-4-methylphenol),2,2'-methylene-bis-(6-tert.butyl-4-ethylphenol), 4,4'-methylene-bis-(6-tert.
butyl-2-methylphenol), 4,L~'-methylene-bis-(2,6-di-tert. ;
butyl-phenol), 2,6-di-(3-tert.butyl-5-methyl-2-hydroxybenzyl)- ~-4-methylphenol, 2,2'-methylene-bis-[4-methyl-6-(~-methylcyclo-hexyl)-phenol], l,l-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 1,1-bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.bu-tyl-4-hydroxyphenyl)-propane, 1,1,3-tris-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.
butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercapto-butane, 1,1,5,5-tetra-(5-tert.butyl-4-hydroxy-2-methylphenyl)-pentane and ethylene-glycol-bis-C3,3-bis-(3'-tert.butyl-4'-hydroxy-phenyl)-butyrate].
1.5 O-, N- and S-benzyl compounds, such as, for example, 3,5,3',5'-tetra-tert.butyl-4,4'-dihydroxydibenzyl ether, 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetic acid octadecyl ester, tris-(3,5-di-tert butyl-4-hydroxybenzyl)-amine and bis-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)-dithioterephthal-ate. ~-1.6 HydroxYbenzylated malonic esters, such as, for example, 2,2-bis-(3,5-di-tert.butyl-2-hydroxybenzyl)-malonic acid dioctadecyl ester, 2-(3-tert.butyl-4-hydroxy-5-methyl-benzyl)-malonic acid dioctadecyl ester, 2,2-bis-(3,5-di-tert.
butyl-4-hydroxybenzyl)-malonic acid di-dodecylmercapto-ethyl-ester and 2,2-bis-(3,5-di-ter-t.butyl-4-hydroxyphenyl)-malonic acid di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]-ester.
1.7 Hydroxybenzyl-aromatics, such as, for example, 1,3,5-'~ '
butyl-2-methylphenol), 4,L~'-methylene-bis-(2,6-di-tert. ;
butyl-phenol), 2,6-di-(3-tert.butyl-5-methyl-2-hydroxybenzyl)- ~-4-methylphenol, 2,2'-methylene-bis-[4-methyl-6-(~-methylcyclo-hexyl)-phenol], l,l-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 1,1-bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.bu-tyl-4-hydroxyphenyl)-propane, 1,1,3-tris-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.
butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercapto-butane, 1,1,5,5-tetra-(5-tert.butyl-4-hydroxy-2-methylphenyl)-pentane and ethylene-glycol-bis-C3,3-bis-(3'-tert.butyl-4'-hydroxy-phenyl)-butyrate].
1.5 O-, N- and S-benzyl compounds, such as, for example, 3,5,3',5'-tetra-tert.butyl-4,4'-dihydroxydibenzyl ether, 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetic acid octadecyl ester, tris-(3,5-di-tert butyl-4-hydroxybenzyl)-amine and bis-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)-dithioterephthal-ate. ~-1.6 HydroxYbenzylated malonic esters, such as, for example, 2,2-bis-(3,5-di-tert.butyl-2-hydroxybenzyl)-malonic acid dioctadecyl ester, 2-(3-tert.butyl-4-hydroxy-5-methyl-benzyl)-malonic acid dioctadecyl ester, 2,2-bis-(3,5-di-tert.
butyl-4-hydroxybenzyl)-malonic acid di-dodecylmercapto-ethyl-ester and 2,2-bis-(3,5-di-ter-t.butyl-4-hydroxyphenyl)-malonic acid di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]-ester.
1.7 Hydroxybenzyl-aromatics, such as, for example, 1,3,5-'~ '
17 .
tri-(3,5-di-tert.butyl-4-hydroxybenzyl~-~,4,6-trimethyl-benzene, 1,4-di-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,3,5,6-te-tramethylbenzene and 2,4,6-tri-(3,5-di-tert.butyl-4-hydroxy-benzyl)-phenol.
1.8 s-Triazine comPounds~ such as, ~or example, 2,4-bis-octylmercapto-6-(3,5-di-tert.butyl-4-hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxy-anilino)-s-triazi.ne, 2-octylmercapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxy-phenoxy)-s-triazine J 2,4,6-tris-(3,5-di-tert.butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.butyl-4-hydr~xyphenylethyl)-s-triazine and 1,3,5-tris- ;
(3,5-di-tert.butyl-4-hydroxybenzyl)-isocyanurate.
1.9 Amides of ~-(3,5-di-tert.but~-4-hydroxyphenyl)-propionic acid, such as, for example, 1,3,5-tris-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine and N,N'-di-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamine.
1 10 Esters of ~-(3,5-di-tert.butvl-4-hydroxyphenyl)-.
propionic acid with monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaeryth-ritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethyl-hexanediol, trime-thylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2?6,7-trioxabicyclo[2,2,2]octane.
1.11. _ters of ~-(5-tert.butyl-4-hydroxy-3-methy]~henyl propionic acid wi-th monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, octadecanol, 1,6-hexanediol,
tri-(3,5-di-tert.butyl-4-hydroxybenzyl~-~,4,6-trimethyl-benzene, 1,4-di-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,3,5,6-te-tramethylbenzene and 2,4,6-tri-(3,5-di-tert.butyl-4-hydroxy-benzyl)-phenol.
1.8 s-Triazine comPounds~ such as, ~or example, 2,4-bis-octylmercapto-6-(3,5-di-tert.butyl-4-hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxy-anilino)-s-triazi.ne, 2-octylmercapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxy-phenoxy)-s-triazine J 2,4,6-tris-(3,5-di-tert.butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.butyl-4-hydr~xyphenylethyl)-s-triazine and 1,3,5-tris- ;
(3,5-di-tert.butyl-4-hydroxybenzyl)-isocyanurate.
1.9 Amides of ~-(3,5-di-tert.but~-4-hydroxyphenyl)-propionic acid, such as, for example, 1,3,5-tris-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine and N,N'-di-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamine.
1 10 Esters of ~-(3,5-di-tert.butvl-4-hydroxyphenyl)-.
propionic acid with monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaeryth-ritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethyl-hexanediol, trime-thylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2?6,7-trioxabicyclo[2,2,2]octane.
1.11. _ters of ~-(5-tert.butyl-4-hydroxy-3-methy]~henyl propionic acid wi-th monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, octadecanol, 1,6-hexanediol,
-18-:. ' . . ~ : . :
1~)48529 l,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodie-thylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, -trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2]octane.
1.12. Esters o~ 3,5-di-tert.butyl-4-hy~drox~phenylacetic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, l,2-propanediol, diethylene glycol, thio-diethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trime-thylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2]octane.
1.13. Acylaminophenols, such as, for example, N-(3,5-di--tert.
butyl-4-hydroxyphenyl)-stearic acid amide and N,Nt-di-(3,5-di-tert.butyl-4-hydroxyphenyl)-thiobis-acetamide.
1.14. Benzylphosphonates, such as, for example, 3,5-di-tert.
butyl-4-hydroxybenzyl-phosphonic acid dimethyl ester, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid diethyl ester, ~ -3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid dioctadecyl ester and 5-tert.butyl-4-hydroxy-3-methylbenzyl-phosphonic acid dioctadecyl ester.
1.15. Aminoaryl derivatives, such as, ~or example, phenyl-l-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p phenyl-enediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-sec.
butyl-p-phenylenediamine~ 6-ethoxy-2,2,4--trimethyl~1,2-dihydro---19-- , , ~)4~S29 qulnoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, monooc-tyllminodibenzyl and dioc-tyliminodibenzyl and polymerised 2,2,4-trimethyl-1,2-dihydroquinoline. Octylated diphenyl-amine, nonylated diphenylamine, N-phenyl-N'-cyclohexyl-p-phenyl-enediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-sec.octyl-p-phenylenediamine, N-phenyl-N-sec.oc-tyl-p-phenylene-diamine, N,N'-di-(1,4-dimethylpentyl)~p phenylenediamine, N,N'-dimethyl-N,N'-di{sec.octyl)-p-phenylenediamine, 2,6-dimethyl-4-methoxyaniline, 4-ethoxy-N-sec.butylaniline, the condensation product of diphenylamine and acetone, and phenothiazine.
2 W absorbers and li~ ~
2.1.2-(2'-Hydroxy~henyl~benztriazoles, such as, for example, -the 5'-methyl-, 3',5'-di-tert.butyl-, 5'-tert.butyl-, 5'-(1,1, 3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.butyl-, 5-chloro-3'-tert.butyl-5'-methyl-, 3'-sec.butyl-5'-tert.butyl-, 3'-a-methylbenzyl-5'-methyl-, 3'-~-me-thylbenzyl-5'-methyl-5-chloro-, 4'-hydrox~y-, 4'-methoxy-, 4'-octox~y-, 3',5'-di-tert.amyl-, 3'-methyl-5'-carbomethoxyethyl- and 5-chloro-3',5'-di-tert.-amyl-derivative.
2.2. 2,4-Bis-(2'-hydrox~phenyl)-6-alk~l-s-triazines, such as, for example, the 6-ethyl-, 6-heptadecyl or 6-undecyl-derivative.
2.3. 2-H~droxy-benzophenones, such as, for exarnple, the 4-hydroxy-, 4-methoxy-, 4-octox~y-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy- or 2'-hydroxy-4,4'-dimethoxy-derivative.
2.4. 1~3-Bis-(2'-hydroxY=be~zoyl~-benzenes, such as, for example, 1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-hydroxy-4'-octyloxy-benzoyl)-benzene and 1~3-bis-(2'-hydroxy-4'-~ 48SZ9 dodccyloxy-benzoyl)-benzene.
2 5 Esters of o~ y____st 1' _ b~ = , such as, for example, phenyl salicylate, octylphenyl salicylate, diben-zoylresorcinol, bis-(4~tert.-butylbenzoyl)-resorcinol, benzoyl-resorcinol and 3,5-di-tert.-butyl-4-hydroxybenzoic acid 2,4-di-tert.butyl-phenyl ester, octadecyl ester or 2-methyl-4,6-di-tert.butyl-phenyl ester.
2.6. Acrylates, such as, for example, ~-cyano-~,~-diphenyl- -acrylic acid ethyl ester or isooctyl ester, ~-carbomethoxy-cinnamic acid methyl ester, ~-cyano-~-methyl-p-methoxy-cinnamic acid methyl ester or butyl es-ter and N-(~-carbomethoxy-vinyl)-2-methyl-indoline.
2.7. Nickel com~ounds, such as,-for example, nickel complexes of 2,2'-thio-bis-[4-(1,1~3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-di-e-thanolamine, nickel cornplexes of bis-[2-hydroxy-4-(1,1,3,3-tetramethylbutyl)-phenyl]-sulphone, such as the 2:1 complex, optionally with addi-tional li~ands such as 2-ethyl-caproic acid, nickel dibutyldithiocarbama-te, nickel salts of 4-hydroxy-3,5-di-tert.butylbenzyl-phosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ket-oximes such as of 2-hydroxy-4-methyl-phenyl-undecylke-tonoxime, nickel 3,5-di-tert.butyl-4-hydroxy-benzoa-te and nickel iso-propylxanthate.
2.8. Stericall~ hindered amines, such as 9 for example, 4-benzoyloxy-2,2,6 7 6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, bis-(2,2,6,6-te-trame-thylpiperi-1~48529 dyl) sebacate, and 3-n--octyl-7~7,9,9-tetramethyl-1,3,8-triaza-spiroC4,5]decane-2,4-dione.
2.9. Oxalic acid.diamides, such as, for example, 4,4'-di-oc-tyl-oxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dime-thylaminopropyl)-oxalamide, 2-ethoxy-5-tert.butyl-2'-ethyl-oxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert.butyl-oxanilide and mixtures of ortho- and para-methoxy- as well as ot o- and p-ethoxy-disubstituted oxanilides, 3. Metal d_activators, such as, for example, oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenyl-hydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide, N,N'-bis-salicyloyl-oxalic acid dihydrazide,N,N'-bis-salicyloyl-hydrazine, N,N'-bis-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hydrazine, N-salicylal-N-salicylidenehydrazine and 3-salicyloyl~nino-1,2,4-triazole.
4. Phosphites, such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-di-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro~5,5 undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl) phosphite.
Compounds which destroy Peroxides~ such as, for example, .
esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole and the zinc salt of 2-Mercapto-benzimidazole.
6. Polyamide stabilisers, such as, for example, copper salts in 1~48529 ~ ::
:
combina-tion with iodides and/or phosphorus compounds and salts ~-of divalent manganese.
7. Basic co-stabilisers, such as, for example, melamine, benzoguanamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, and alkali metal salts and alkaline earth metal salts of higher fa-tty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K
palmitate, antimony pyrocatecholate or zinc pyrocatecholate, 8, PVC stabilisers, such as, for example, OrganiG tin compounds, , organic lead compounds and barium-cadmium salts of fatty acids, ~-9, Nucleating a~ents, such as, for example, 4-tert,butyl-benzoie acid, adipic acid and diphenylacetic aeid.
10, Urea derivatives, such as, for example, N-cyclohexyl-N'~
:: .
naphthylurea, N-phenyl-N,N'-dicyclohexylurea, N-phenyl-N'-2 naphthylurea, N-phenylthiourea and N,N'-dibutylthiourea.
11, 0-ther additives, such as, for example, plasticisers, lubricants, emulsifiers, fillers, carbon black, asbestos, kaolin, talc, glass fibres, plgments, optical brighteners~
flameproofing agents and antistatic agents, The preparation and use of the compounds according to the invention are described in greater detail in the examples which follow, In these, parts denote parts by weight and %
denotes percentages by weight, 1C~485Z9 ~
Example 1 46 g (0.64 mol) of isobu-tyraldehyde and 184 g (0.5 mol) of N,N-diethyl-dithiocarbamic acid (3,5-di-tert butyl-4-hydroxybenzyl) ester are dissolved in 600 ml of isopropanol at 60C. A solution of 20 g (0.5 mol) of sodium hydroxide in 50 ml of wa-ter is added dropwise at this temperature, with stirring, over the course of one hour. The mix-ture is -then heated for 2 hours un1er r~luxand ~x~d-to 50~ and 600ml~of 1% s~eng~
acetic acid are added and the whole is cooled to 0C, whereupon the product crystallises. After being filtered off with suction, 133 g (92% of -theory) of 3-(3,5-di-tert.butyl-4-hydroxyphenyl)-2,2-dime-thyL~propionaldehyde are obtained. Af-ter recrystallis-ation from 66% strength isopropanol, the product melts at 78C.
If, in this example, the isobutyraldehyde is replaced by an equimolecular quan-tity of one of the aldehydes in Table I which follows, an otherwise identical procedure gives the 2-(3,5-di-tert.-butyl-4-hydroxybenzyl)-substituted aldehydes with the melting points shown: -1q)48SZ9 T a b l e Melting point of the Aldehyde benzylatlon product 2~5 .
. . liquid ~) - C~lO :-Cl~O 66C
., .
H /CIIQ
\/
/C\ 92C
f~2 ` Ic~l2 C~2 ~C 12 Cli2 .
fH3 90C
ll- C ~ CHO
_ ~) Analysls Calculated C 79.71 H 11.05 0 9.2 Found 79.7 11.1 9.1 __ .
:
1~48SZ9 Exan?ple 2 206 g (1 mol) of 2,6-di-ter-t.butylphenol~ 30 g (1 mol) of paraformaldehyde and 76.1 g (1 mol) of carbon disul-phide are su-pended in 350 ml of isopropanol. 7~.15 g (1 mol) of diethylarnine, dissolved in 125 ml of isopropanol, are then a~d~x~se with stirring over the course of or.e hour. The reaction is exothermic and the reaction mix-ture heats up from room tempera-ture to approx. 40C. It is then heated under reflux and stirred for a further 3 hours at this -temperature.
It is then cooled to 50C~ 92 g (approx. 1.3 mols) of isobuty-raldehyde are added and a solution of 40 g of sodium hydroxide in 100 ml of water is added dropwise over the course of one hour. Further working up is carried ou-t according to Example 1. 3-(3,5-Ditert.butyl-4-hydroxyphenyl)-2,2-dimethyl-propionaldehyde, melting point 76~78C, is thus obtained in an almost quantitative yield.
If, in this exarnple, the 2,6-d~tert.-butylphenol is replaced by an equimolecular quantity of one of the phenols in Table II which follows, an otherwise identical procedure gives the 3-(3,5-dialkyl-4-hydroxyphenyl)-2,2-dimethyl-propionaldehydes with the melting points shown:
-26-~
. ., ~1)485Z9 T a b 1 e II
. , ~
Melting point of the -:
Phenol reaction product _. , iso-Propyl U ~ 1 71C
o-Propyl . ~.
C~3 `
. ~ .
HO ~ ~ 7~ C
/~~
.
, ~27-.
, lV4~S;i~9 E~cam~le ~
- 14 g (0.35 mol) o~ sodi~ml hydroxide are dissolved in 14 ml of water and are run in-to a suspension of 1.5 g of tetrabutylammonium iodide in 20 ml of benzene. The mixture is hea-ted to 70C with stirring and a solution of 76.5 g (0 3 mol) of 3,5-di~tert.butyl-4-hydroxy-benzyl chloride and 28.8 g (0.4 mol) of isobutyraldehyde in 100 ml of ligroin is added dropwise a-t this temperature over the course of 2 hours. The mixture is stirred for a further 2 hours at 70Cand is then cooled, 10 ml of glacial acetic acid are added and the mix-ture is diluted with 100 ml of toluene. The organic phase is thoroughly washed with water and is completely evaporated under reduced pressure. A red-brown oil is thus obtained, which, according to thin-layer chromatography (migrating agen-t toluene), contains 3-(3,5-di tert.butyl-4-hydroxyphenyl)-2,2-dime-thyl-propionaldehyde.
Example 4 23.2 g (0.08 mol) of 3-(3,5-di-tert.butyl-4-hydroxy-phenyl)-2,2-dimethyl-propionaldehyde, 3.92 g (0.08 mol) of sodium cyanide and 23 g (0.24 mol) of ammonium carbonate are suspended in 100 ml of 90% strength ethanol and are s-tirred for 2 hours at 45 C. The mix-ture is then cooled -to room temperature, treated with 200 ml of water and stirred Yor a further hour. The precipitate which has formed is then filtered off with suction,washed with a ~e ar~ount of water and recrystallised from acetonitrile. The 5-Cl,l-dirnethyl-2 (3,5-di-tert.butyl-4-hydrox~phenyl)-ethyl]-hydantoin thus ..
, : .
10~
ob-tained sinters from 150C 7 becomes solid again and then mel-ts from 220C.
Example 5 Stabilisation of polypropylene against degradation during ~__ces.sin _ _ O.1 pa-rt of 3-(395-di-tert.butyl-4-hydro~yphenyl)-2,2-dime-th~Jl-propionaldehyde are homogeneously mixed wi-th 100 parts of polypropylene powder ("Propathene HF 20" of Messrs. ICI) and are regranulated 5 times in succession in a single~screw extruder at a maximum of 260C and 100 rpm.
The melt index (MI) of the material is measured in each case after the lst-, 3rd and 5th extrusion (2,160 g through-put at 230C; data in grams every 10 minutes). A degradation of -the polymer manifes-ts itself in a rapid increase in the melt index. A parallel experiment is carried out in the same manner with no stabiliser added.
T a b 1 e III
. _ .
Melt index Ini-tial 1st 3rd 5-th state Extrusion Extrusion Ex-trusion . _ __ . _ Unstabilised sample 2.50 12.0 34.7 73.3 Stabilised sample 2.50 3.5 5.8 6.1 i~48S29 Exam 36.7 g (0.1 mol) of N9N-dlethyl~di-thiocarbamic acid (3,5-di-tert.butyl-4-hydroxybenzyl) ester and 3.5 g (0.6 mol) of propionaldehyde in 120 mi of isopropanol are initially --taken and are warmed to 40C. A solution of sodium hydroxide in 10 ml of water is added dropwise with s-tirring over the course of one hour. S-tirring is continued for a further 2 hours at the same temperature. The mixture is -then cooled to room temperature and 30 ml of 10% streng-th acetic acid are added. The precipitate which has formed is filtered off with suction and thoroughly washed, first with 70% streng-th iso-propanol and then with 1~ strength acetic acid. After recrystallisa-tion from acetonitrile, the 2,2-bis-(3,5-di-tert.bu-tyl-4-hydroxybenzyl)-propionaldehyde melts at 173C.
Example 7 46 g (0.64 mol) of isobu-tyraldehyde and 161.5 g (0.5 mol) of N,N-diethyl-dithiocarbamic acid (~-tert.-butyl-4-hydroxy-5-methyl-benzyl) ester are dissolved in 600 ml of isopropanol at 60C.-A solution of 20 g (0.5 mol) of sodium hydroxide in 50 ml of wa-ter is added dropwise at this tempera-tureJ with stirring, o~er the course of o~ hour. The mixture is then heated under reflux for 2 hours. After distilling off approx. 200 ml of isopropanol, the mixture is treated with 2 ml of g~acial acetic acid and 400 ml of water are then added, whereupon the product crystallises. After filtering off with suction, it is recrystallised from a 5:2 mixture of isopropanol/
water. 3-(3-Tert.-bu-tyl-4-hydroxy-5-methylphenyl)-2,2-dimethyl-, . " . ' ,:
... . .
1~348S29 propionaldehyde, mel-ting poin~t 93C, ls thus obtained If 7 in -this example, -the N,N-di.ethyl-di-thiocarbamic acid (3-tert.butyl-4-hydro.xy-5-methylbenzyl) ester is replaced by one of the nuclear-substituted die-thyldithiocar~amic acid (4-hydroxybenzyl) esters in Table IV which follows, an o-ther-wise identical procedure gives -the nuclear-substituted-3-(4 hydroxyphenyl)-2,2-dimethyl-propionaldehydes with the melting points shown:
. T a b l e _ IV
Dithiocarbamic acid ester product _ _ _ . . . .
tert.Butyl H0 ~ ~ -Cll2S-C-N / ¦ 102C
C~3 CU3 ,' ' . .~
H2C _cu~
H~G CH2 S
N \ 92C
--~ C 2H5 H2C CH2 .
1~)48529 l,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodie-thylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, -trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2]octane.
1.12. Esters o~ 3,5-di-tert.butyl-4-hy~drox~phenylacetic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, l,2-propanediol, diethylene glycol, thio-diethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trime-thylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2]octane.
1.13. Acylaminophenols, such as, for example, N-(3,5-di--tert.
butyl-4-hydroxyphenyl)-stearic acid amide and N,Nt-di-(3,5-di-tert.butyl-4-hydroxyphenyl)-thiobis-acetamide.
1.14. Benzylphosphonates, such as, for example, 3,5-di-tert.
butyl-4-hydroxybenzyl-phosphonic acid dimethyl ester, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid diethyl ester, ~ -3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid dioctadecyl ester and 5-tert.butyl-4-hydroxy-3-methylbenzyl-phosphonic acid dioctadecyl ester.
1.15. Aminoaryl derivatives, such as, ~or example, phenyl-l-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p phenyl-enediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-sec.
butyl-p-phenylenediamine~ 6-ethoxy-2,2,4--trimethyl~1,2-dihydro---19-- , , ~)4~S29 qulnoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, monooc-tyllminodibenzyl and dioc-tyliminodibenzyl and polymerised 2,2,4-trimethyl-1,2-dihydroquinoline. Octylated diphenyl-amine, nonylated diphenylamine, N-phenyl-N'-cyclohexyl-p-phenyl-enediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-sec.octyl-p-phenylenediamine, N-phenyl-N-sec.oc-tyl-p-phenylene-diamine, N,N'-di-(1,4-dimethylpentyl)~p phenylenediamine, N,N'-dimethyl-N,N'-di{sec.octyl)-p-phenylenediamine, 2,6-dimethyl-4-methoxyaniline, 4-ethoxy-N-sec.butylaniline, the condensation product of diphenylamine and acetone, and phenothiazine.
2 W absorbers and li~ ~
2.1.2-(2'-Hydroxy~henyl~benztriazoles, such as, for example, -the 5'-methyl-, 3',5'-di-tert.butyl-, 5'-tert.butyl-, 5'-(1,1, 3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.butyl-, 5-chloro-3'-tert.butyl-5'-methyl-, 3'-sec.butyl-5'-tert.butyl-, 3'-a-methylbenzyl-5'-methyl-, 3'-~-me-thylbenzyl-5'-methyl-5-chloro-, 4'-hydrox~y-, 4'-methoxy-, 4'-octox~y-, 3',5'-di-tert.amyl-, 3'-methyl-5'-carbomethoxyethyl- and 5-chloro-3',5'-di-tert.-amyl-derivative.
2.2. 2,4-Bis-(2'-hydrox~phenyl)-6-alk~l-s-triazines, such as, for example, the 6-ethyl-, 6-heptadecyl or 6-undecyl-derivative.
2.3. 2-H~droxy-benzophenones, such as, for exarnple, the 4-hydroxy-, 4-methoxy-, 4-octox~y-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy- or 2'-hydroxy-4,4'-dimethoxy-derivative.
2.4. 1~3-Bis-(2'-hydroxY=be~zoyl~-benzenes, such as, for example, 1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-hydroxy-4'-octyloxy-benzoyl)-benzene and 1~3-bis-(2'-hydroxy-4'-~ 48SZ9 dodccyloxy-benzoyl)-benzene.
2 5 Esters of o~ y____st 1' _ b~ = , such as, for example, phenyl salicylate, octylphenyl salicylate, diben-zoylresorcinol, bis-(4~tert.-butylbenzoyl)-resorcinol, benzoyl-resorcinol and 3,5-di-tert.-butyl-4-hydroxybenzoic acid 2,4-di-tert.butyl-phenyl ester, octadecyl ester or 2-methyl-4,6-di-tert.butyl-phenyl ester.
2.6. Acrylates, such as, for example, ~-cyano-~,~-diphenyl- -acrylic acid ethyl ester or isooctyl ester, ~-carbomethoxy-cinnamic acid methyl ester, ~-cyano-~-methyl-p-methoxy-cinnamic acid methyl ester or butyl es-ter and N-(~-carbomethoxy-vinyl)-2-methyl-indoline.
2.7. Nickel com~ounds, such as,-for example, nickel complexes of 2,2'-thio-bis-[4-(1,1~3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-di-e-thanolamine, nickel cornplexes of bis-[2-hydroxy-4-(1,1,3,3-tetramethylbutyl)-phenyl]-sulphone, such as the 2:1 complex, optionally with addi-tional li~ands such as 2-ethyl-caproic acid, nickel dibutyldithiocarbama-te, nickel salts of 4-hydroxy-3,5-di-tert.butylbenzyl-phosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ket-oximes such as of 2-hydroxy-4-methyl-phenyl-undecylke-tonoxime, nickel 3,5-di-tert.butyl-4-hydroxy-benzoa-te and nickel iso-propylxanthate.
2.8. Stericall~ hindered amines, such as 9 for example, 4-benzoyloxy-2,2,6 7 6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, bis-(2,2,6,6-te-trame-thylpiperi-1~48529 dyl) sebacate, and 3-n--octyl-7~7,9,9-tetramethyl-1,3,8-triaza-spiroC4,5]decane-2,4-dione.
2.9. Oxalic acid.diamides, such as, for example, 4,4'-di-oc-tyl-oxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dime-thylaminopropyl)-oxalamide, 2-ethoxy-5-tert.butyl-2'-ethyl-oxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert.butyl-oxanilide and mixtures of ortho- and para-methoxy- as well as ot o- and p-ethoxy-disubstituted oxanilides, 3. Metal d_activators, such as, for example, oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenyl-hydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide, N,N'-bis-salicyloyl-oxalic acid dihydrazide,N,N'-bis-salicyloyl-hydrazine, N,N'-bis-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hydrazine, N-salicylal-N-salicylidenehydrazine and 3-salicyloyl~nino-1,2,4-triazole.
4. Phosphites, such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-di-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro~5,5 undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl) phosphite.
Compounds which destroy Peroxides~ such as, for example, .
esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole and the zinc salt of 2-Mercapto-benzimidazole.
6. Polyamide stabilisers, such as, for example, copper salts in 1~48529 ~ ::
:
combina-tion with iodides and/or phosphorus compounds and salts ~-of divalent manganese.
7. Basic co-stabilisers, such as, for example, melamine, benzoguanamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, and alkali metal salts and alkaline earth metal salts of higher fa-tty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K
palmitate, antimony pyrocatecholate or zinc pyrocatecholate, 8, PVC stabilisers, such as, for example, OrganiG tin compounds, , organic lead compounds and barium-cadmium salts of fatty acids, ~-9, Nucleating a~ents, such as, for example, 4-tert,butyl-benzoie acid, adipic acid and diphenylacetic aeid.
10, Urea derivatives, such as, for example, N-cyclohexyl-N'~
:: .
naphthylurea, N-phenyl-N,N'-dicyclohexylurea, N-phenyl-N'-2 naphthylurea, N-phenylthiourea and N,N'-dibutylthiourea.
11, 0-ther additives, such as, for example, plasticisers, lubricants, emulsifiers, fillers, carbon black, asbestos, kaolin, talc, glass fibres, plgments, optical brighteners~
flameproofing agents and antistatic agents, The preparation and use of the compounds according to the invention are described in greater detail in the examples which follow, In these, parts denote parts by weight and %
denotes percentages by weight, 1C~485Z9 ~
Example 1 46 g (0.64 mol) of isobu-tyraldehyde and 184 g (0.5 mol) of N,N-diethyl-dithiocarbamic acid (3,5-di-tert butyl-4-hydroxybenzyl) ester are dissolved in 600 ml of isopropanol at 60C. A solution of 20 g (0.5 mol) of sodium hydroxide in 50 ml of wa-ter is added dropwise at this temperature, with stirring, over the course of one hour. The mix-ture is -then heated for 2 hours un1er r~luxand ~x~d-to 50~ and 600ml~of 1% s~eng~
acetic acid are added and the whole is cooled to 0C, whereupon the product crystallises. After being filtered off with suction, 133 g (92% of -theory) of 3-(3,5-di-tert.butyl-4-hydroxyphenyl)-2,2-dime-thyL~propionaldehyde are obtained. Af-ter recrystallis-ation from 66% strength isopropanol, the product melts at 78C.
If, in this example, the isobutyraldehyde is replaced by an equimolecular quan-tity of one of the aldehydes in Table I which follows, an otherwise identical procedure gives the 2-(3,5-di-tert.-butyl-4-hydroxybenzyl)-substituted aldehydes with the melting points shown: -1q)48SZ9 T a b l e Melting point of the Aldehyde benzylatlon product 2~5 .
. . liquid ~) - C~lO :-Cl~O 66C
., .
H /CIIQ
\/
/C\ 92C
f~2 ` Ic~l2 C~2 ~C 12 Cli2 .
fH3 90C
ll- C ~ CHO
_ ~) Analysls Calculated C 79.71 H 11.05 0 9.2 Found 79.7 11.1 9.1 __ .
:
1~48SZ9 Exan?ple 2 206 g (1 mol) of 2,6-di-ter-t.butylphenol~ 30 g (1 mol) of paraformaldehyde and 76.1 g (1 mol) of carbon disul-phide are su-pended in 350 ml of isopropanol. 7~.15 g (1 mol) of diethylarnine, dissolved in 125 ml of isopropanol, are then a~d~x~se with stirring over the course of or.e hour. The reaction is exothermic and the reaction mix-ture heats up from room tempera-ture to approx. 40C. It is then heated under reflux and stirred for a further 3 hours at this -temperature.
It is then cooled to 50C~ 92 g (approx. 1.3 mols) of isobuty-raldehyde are added and a solution of 40 g of sodium hydroxide in 100 ml of water is added dropwise over the course of one hour. Further working up is carried ou-t according to Example 1. 3-(3,5-Ditert.butyl-4-hydroxyphenyl)-2,2-dimethyl-propionaldehyde, melting point 76~78C, is thus obtained in an almost quantitative yield.
If, in this exarnple, the 2,6-d~tert.-butylphenol is replaced by an equimolecular quantity of one of the phenols in Table II which follows, an otherwise identical procedure gives the 3-(3,5-dialkyl-4-hydroxyphenyl)-2,2-dimethyl-propionaldehydes with the melting points shown:
-26-~
. ., ~1)485Z9 T a b 1 e II
. , ~
Melting point of the -:
Phenol reaction product _. , iso-Propyl U ~ 1 71C
o-Propyl . ~.
C~3 `
. ~ .
HO ~ ~ 7~ C
/~~
.
, ~27-.
, lV4~S;i~9 E~cam~le ~
- 14 g (0.35 mol) o~ sodi~ml hydroxide are dissolved in 14 ml of water and are run in-to a suspension of 1.5 g of tetrabutylammonium iodide in 20 ml of benzene. The mixture is hea-ted to 70C with stirring and a solution of 76.5 g (0 3 mol) of 3,5-di~tert.butyl-4-hydroxy-benzyl chloride and 28.8 g (0.4 mol) of isobutyraldehyde in 100 ml of ligroin is added dropwise a-t this temperature over the course of 2 hours. The mixture is stirred for a further 2 hours at 70Cand is then cooled, 10 ml of glacial acetic acid are added and the mix-ture is diluted with 100 ml of toluene. The organic phase is thoroughly washed with water and is completely evaporated under reduced pressure. A red-brown oil is thus obtained, which, according to thin-layer chromatography (migrating agen-t toluene), contains 3-(3,5-di tert.butyl-4-hydroxyphenyl)-2,2-dime-thyl-propionaldehyde.
Example 4 23.2 g (0.08 mol) of 3-(3,5-di-tert.butyl-4-hydroxy-phenyl)-2,2-dimethyl-propionaldehyde, 3.92 g (0.08 mol) of sodium cyanide and 23 g (0.24 mol) of ammonium carbonate are suspended in 100 ml of 90% strength ethanol and are s-tirred for 2 hours at 45 C. The mix-ture is then cooled -to room temperature, treated with 200 ml of water and stirred Yor a further hour. The precipitate which has formed is then filtered off with suction,washed with a ~e ar~ount of water and recrystallised from acetonitrile. The 5-Cl,l-dirnethyl-2 (3,5-di-tert.butyl-4-hydrox~phenyl)-ethyl]-hydantoin thus ..
, : .
10~
ob-tained sinters from 150C 7 becomes solid again and then mel-ts from 220C.
Example 5 Stabilisation of polypropylene against degradation during ~__ces.sin _ _ O.1 pa-rt of 3-(395-di-tert.butyl-4-hydro~yphenyl)-2,2-dime-th~Jl-propionaldehyde are homogeneously mixed wi-th 100 parts of polypropylene powder ("Propathene HF 20" of Messrs. ICI) and are regranulated 5 times in succession in a single~screw extruder at a maximum of 260C and 100 rpm.
The melt index (MI) of the material is measured in each case after the lst-, 3rd and 5th extrusion (2,160 g through-put at 230C; data in grams every 10 minutes). A degradation of -the polymer manifes-ts itself in a rapid increase in the melt index. A parallel experiment is carried out in the same manner with no stabiliser added.
T a b 1 e III
. _ .
Melt index Ini-tial 1st 3rd 5-th state Extrusion Extrusion Ex-trusion . _ __ . _ Unstabilised sample 2.50 12.0 34.7 73.3 Stabilised sample 2.50 3.5 5.8 6.1 i~48S29 Exam 36.7 g (0.1 mol) of N9N-dlethyl~di-thiocarbamic acid (3,5-di-tert.butyl-4-hydroxybenzyl) ester and 3.5 g (0.6 mol) of propionaldehyde in 120 mi of isopropanol are initially --taken and are warmed to 40C. A solution of sodium hydroxide in 10 ml of water is added dropwise with s-tirring over the course of one hour. S-tirring is continued for a further 2 hours at the same temperature. The mixture is -then cooled to room temperature and 30 ml of 10% streng-th acetic acid are added. The precipitate which has formed is filtered off with suction and thoroughly washed, first with 70% streng-th iso-propanol and then with 1~ strength acetic acid. After recrystallisa-tion from acetonitrile, the 2,2-bis-(3,5-di-tert.bu-tyl-4-hydroxybenzyl)-propionaldehyde melts at 173C.
Example 7 46 g (0.64 mol) of isobu-tyraldehyde and 161.5 g (0.5 mol) of N,N-diethyl-dithiocarbamic acid (~-tert.-butyl-4-hydroxy-5-methyl-benzyl) ester are dissolved in 600 ml of isopropanol at 60C.-A solution of 20 g (0.5 mol) of sodium hydroxide in 50 ml of wa-ter is added dropwise at this tempera-tureJ with stirring, o~er the course of o~ hour. The mixture is then heated under reflux for 2 hours. After distilling off approx. 200 ml of isopropanol, the mixture is treated with 2 ml of g~acial acetic acid and 400 ml of water are then added, whereupon the product crystallises. After filtering off with suction, it is recrystallised from a 5:2 mixture of isopropanol/
water. 3-(3-Tert.-bu-tyl-4-hydroxy-5-methylphenyl)-2,2-dimethyl-, . " . ' ,:
... . .
1~348S29 propionaldehyde, mel-ting poin~t 93C, ls thus obtained If 7 in -this example, -the N,N-di.ethyl-di-thiocarbamic acid (3-tert.butyl-4-hydro.xy-5-methylbenzyl) ester is replaced by one of the nuclear-substituted die-thyldithiocar~amic acid (4-hydroxybenzyl) esters in Table IV which follows, an o-ther-wise identical procedure gives -the nuclear-substituted-3-(4 hydroxyphenyl)-2,2-dimethyl-propionaldehydes with the melting points shown:
. T a b l e _ IV
Dithiocarbamic acid ester product _ _ _ . . . .
tert.Butyl H0 ~ ~ -Cll2S-C-N / ¦ 102C
C~3 CU3 ,' ' . .~
H2C _cu~
H~G CH2 S
N \ 92C
--~ C 2H5 H2C CH2 .
Claims (41)
1. Compounds of the general formula I
(I) in which R1 and R5 independently of one another denote hydrogen or methyl, or R1 conjointly with R2 and/
or R4 conjointly with R5 denotes tetramethylene, R2 denotes alkyl, cycloalkyl or aralkyl, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl, cycloalkyl or aralkyl, R6 denotes alkyl, aralkyl, acyloxyalkyl, oxaalkyl or phenyl, R7 denotes alkyl, phenyl or the group in which R1 to R5 have the indicated meaning, or, conjointly with R6,denotes alkylene, and n denotes o or 1.
(I) in which R1 and R5 independently of one another denote hydrogen or methyl, or R1 conjointly with R2 and/
or R4 conjointly with R5 denotes tetramethylene, R2 denotes alkyl, cycloalkyl or aralkyl, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl, cycloalkyl or aralkyl, R6 denotes alkyl, aralkyl, acyloxyalkyl, oxaalkyl or phenyl, R7 denotes alkyl, phenyl or the group in which R1 to R5 have the indicated meaning, or, conjointly with R6,denotes alkylene, and n denotes o or 1.
2. Compounds according to Claim 1 of the formula I in which R1 and R5 independently of one another denote hydrogen or methyl, or R1 conjointly with R2 and/or R4 conjointly with R5 denotes tetramethylene, R2 denotes alkyl with 1 to 8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl with 1 to 8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, R6 denotes alkyl with 1 to 8 carbon atoms, R7 denotes alkyl with 1 to 8 carbon atoms or the group in which R1 to R5 have the indicated meaning, or, conjointly with R6,denotes alkylene with 2 to 11 carbon atoms, and n denotes o or 1.
3. Compounds according to Claim 1 of the formula I in which R1 and R5 independently of one another denote hydrogen or methyl, R2 denotes alkyl with 1-4 carbon atoms, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms, R6 denotes alkyl with 1 to 4 carbon atoms, R7 denotes alkyl with 1-4 carbon atoms or the group in which R1 to R5 have the indicated meaning, or, con-jointly with R6, denotes alkylene with 4 or 5 carbon atoms, and n denotes 0 or 1.
4. Compounds according to Claim 1 of the formula I in which R1 denotes hydrogen or methyl, R2 denotes alkyl with 1-4 carbon atoms or, conjointly with RI denotes tetramethylene, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms or, conjointly with R5, denotes tetramethylene, R5 denotes hydrogen, R6 denotes alkyl with 1 to 4 carbon atoms or phenyl, R7 denotes alkyl with 1 or 2 carbon atoms or the group in which R1 to R5 have the indicated meaning, or, conjointly with R6,denotes alkylene with 5 carbon atoms, and n denotes 1.
5. Compounds according to Claim 1 of the formula I in which R1 denotes hydrogen or methyl, R2 denotes alkyl with 1-4 carbon atoms, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms, R5 denotes hydrogen, R6 denotes alkyl with 1 to 4 carbon atoms, R7 denotes alkyl with 1 or 2 carbon atoms or the group in which R1 to R5 have the indicated meaning, or, conjointly with R6, denotes alkylene with 5 carbon atoms, and n denotes 1,
6. Compounds according to Claim 2 of the formula I in which n denotes the number 1.
7. Compound of Claim 1 of the formula
8. Compound of Claim 1 of the formula
9. Compound of Claim 1 of the formula
10. Compound of Claim 1 of the formula
11. Compound of Claim 1 of the formula
12. Process for the manufacture of compounds of the general formula Ic (Ic) in which R1 denotes hydrogen or conjointly with R? denotes tetramethylene, R5 denotes hydrogen or methyl or conjointly with R? denotes tetramethylene, R? and R? independently of one another denote alkyl, cycloalkyl or aralkyl, R6 denotes alkyl, and R7 denotes alkyl or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene, characterised in that a compound of the formula V
(V) wherein R1, R?, R? and R5 have the meaning defined in formula Ic and R8 and Rg independently of one another denote alkyl or conjointly, with the inclusion of the nitrogen atom, denote a saturated heterocyclic 5- or 6-membered ring, are reacted with a compound of the formula VI
(VI) wherein R? denotes alkyl and R? denotes hydrogen or alkyl or conjointly with R? denotes alkylene, in the presence of a base and in a solvent.
(V) wherein R1, R?, R? and R5 have the meaning defined in formula Ic and R8 and Rg independently of one another denote alkyl or conjointly, with the inclusion of the nitrogen atom, denote a saturated heterocyclic 5- or 6-membered ring, are reacted with a compound of the formula VI
(VI) wherein R? denotes alkyl and R? denotes hydrogen or alkyl or conjointly with R? denotes alkylene, in the presence of a base and in a solvent.
13. Process according to Claim 12, characterised in that, in the general formula Ic, R1 denotes hydrogen, R5 denotes hydrogen or methyl and the remaining symbols are defined as in Claim 12.
14. Process according to Claim 13, characterised in that compounds of the formula V are used in which R8 and R9 indepen-dently of one another denote alkyl with 1 to 5 carbon atoms or conjointly, with the inclusion of the nitrogen atom, denote the radical of morpholine or piperidine.
15. Process according to Claim 13, characterised in that compounds of the formula V are used in which R8 and R9 denote methyl or ethyl.
16. Process according to Claim 13, characterised in that alkali metal hydroxides, alcoholates or hydrides are used as the base.
17. Process according to Claim 13, characterised in that aqueous alkali metal hydroxide solutions are used as the base.
18. Process according to Claim 13, characterised in that the solvents used are miscible with water.
19. Process according to Claim 18, characterised in that methanol, ethanol or isopropanol is used.
20. Modification of the process according to Claim 12 for the manufacture of compounds of the general formula Ic in which R6 and R7 independently of one another denote alkyl or conjointly denote alkylene and the remaining symbols are def-ined as under formula Ic, characterised in that a compound of the formula VII
(VII) in which R1 denotes hydrogen or conjointly with R2 denotes tetramethylene, R5 denotes hydrogen or methyl or conjointly with R4 denotes tetramethylene, R2 and R4 independently of one another denote alkyl, cycloalkyl or aralkyl, is reacted in a solvent with carbon disulphide, a formaldehyde donor and a secondary amine of the formula VIII
(VIII) in which R8 and R9 independently of one another denote alkyl or conjointly, with the inclusion of the nitrogen atom, denote a saturated heterocyclic 5- or 6-membered ring, and the reac-tion is subsequently brought to completion in the presence of a base by adding a compound of the formula VI.
(VII) in which R1 denotes hydrogen or conjointly with R2 denotes tetramethylene, R5 denotes hydrogen or methyl or conjointly with R4 denotes tetramethylene, R2 and R4 independently of one another denote alkyl, cycloalkyl or aralkyl, is reacted in a solvent with carbon disulphide, a formaldehyde donor and a secondary amine of the formula VIII
(VIII) in which R8 and R9 independently of one another denote alkyl or conjointly, with the inclusion of the nitrogen atom, denote a saturated heterocyclic 5- or 6-membered ring, and the reac-tion is subsequently brought to completion in the presence of a base by adding a compound of the formula VI.
21. Process according to Claim 20, characterised in that, in formula Ic, R1 denotes hydrogen and R5 denotes hydrogen or methyl, and the remaining symbols are defined as in the formula Ic.
22. Process according to Claim 21, characterised in that an aqueous formaldehyde solution is used as the formaldehyde donor.
23. Process according to Claim 21, characterised in that paraformaldehyde is used as the formaldehyde donor.
24. Process according to Claim 21, characterised in that a compound in which R8 and R9 independently of one another denote alkyl with 1 to 5 carbon atoms or conjointly, with the inclusion of the nitrogen atom, denote the radical of morpholine or piperidine, is used as the secondary amine of the formula VIII.
25. Process according to Claim 24, characterised in that R8 and R9 denote methyl or ethyl.
26. Compositions of matter consisting of a polymeric sub-strate and a compound of the general formula I
(I) in which R1 and R5 independently of one another denote hydro-gen or methyl, or R1 conjointly with R2 denotes tetramethylene and/or R4 conjointly with R5 denotes tetramethylene, R2 denotes alkyl, cycloalkyl or aralkyl, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl, cycloalkyl or aralkyl, R6 denotes alkyl, aralkyl, acyloxyalkyl, oxaalkyl or phenyl, R7 denotes alkyl, phenyl or the group in which R1 to R5 have the indicated meaning, or R7 con-jointly with R6 denotes alkylene, and n denotes 0 or 1,
(I) in which R1 and R5 independently of one another denote hydro-gen or methyl, or R1 conjointly with R2 denotes tetramethylene and/or R4 conjointly with R5 denotes tetramethylene, R2 denotes alkyl, cycloalkyl or aralkyl, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl, cycloalkyl or aralkyl, R6 denotes alkyl, aralkyl, acyloxyalkyl, oxaalkyl or phenyl, R7 denotes alkyl, phenyl or the group in which R1 to R5 have the indicated meaning, or R7 con-jointly with R6 denotes alkylene, and n denotes 0 or 1,
27. Compositions of matter according to Claim 26, charac-terised in that, in the formula I, R1 and R5 independently of one another denote hydrogen or methyl, or R1 conjointly with R2 denotes tetramethylene and/or R4 conjointly with R5 denotes tetramethylene, R2 denotes alkyl with 1 to 8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl with 1 to 8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, R6 denotes alkyl with 1 to 8 carbon atoms, R7 denotes alkyl with 1 to 8 carbon atoms or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene with 2 to 11 carbon atoms, and n denotes 0 or 1.
28. Compositions of matter according to Claim 26, charac-terised in that, in the formula I, R1 and R5 independently of one another denote hydrogen or methyl, R2 denotes alkyl with 1-4 carbon atoms, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms, R6 denotes alkyl with 1 to 4 carbon atoms, R7 denotes alkyl with 1.-4 carbon atoms or the group in which R1 to R5 have the indicated meaning, or R7 con-jointly with R6 denotes alkylene with 4 or 5 carbon atoms, and n denotes 0 or 1
29. Compositions of matter according to Claim 26, charac-terised in that, in formula I, R1 denotes hydrogen or methyl, R2 denotes alkyl with 1-4 carbon atoms or conjointly with R1 denotes tetramethylene, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms, or conjointly with R5 denotes tetra-methylene, R5 denotes hydrogen, R6 denotes alkyl with 1 to 4 carbon atoms or phenyl, R7 denotes alkyl with 1 or 2 carbon atoms or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene with 5 carbon atoms, and n denotes 1.
30. Composition of matter according to Claim 26, charac-terised in that, in the formula I, R1 denotes hydrogen or methyl, R2 denotes alkyl with 1-4 carbon atoms, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms, R5 denotes hydrogen, R6 denotes alkyl with 1 to 4 carbon atoms, R7 denotes alkyl with 1 or 2 carbon atoms or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene with 5 carbon atoms, and n denotes 1.
31. Compositions of matter according to claim 27, characterized in that, in formula I, n denotes the number 1.
32. Compositions of matter according to claim 26, characterized in that the polymer of the substrate is a polyolefine.
33. Compositions of matter according to claim 32 characterized in that the polyolefine is polypropylene.
34. Process for the protection of organic polymers which are sensitive to oxidation, characterized in that a compound of the general formula I
(I) in which R1 and R5 independently of one another denote hydrogen or methyl or R1 conjointly with R2 denotes tetramethylene and/or R4 conjointly with R5 denotes tetramethylene, R2 denotes alkyl, cycloalkyl or aralkyl, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl, cycloalkyl or aralkyl, R6 denotes alkyl, aralkyl, acyloxyalkyl, oxaalkyl or phenyl, R7 denotes alkyl, phenyl or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene, and n denotes 0 or 1, is incorporated into these organic substrates.
(I) in which R1 and R5 independently of one another denote hydrogen or methyl or R1 conjointly with R2 denotes tetramethylene and/or R4 conjointly with R5 denotes tetramethylene, R2 denotes alkyl, cycloalkyl or aralkyl, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl, cycloalkyl or aralkyl, R6 denotes alkyl, aralkyl, acyloxyalkyl, oxaalkyl or phenyl, R7 denotes alkyl, phenyl or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene, and n denotes 0 or 1, is incorporated into these organic substrates.
35. Process according to claim 34, characterized in that a compound of the formula I in which R1 and R5 independently of one another denote hydrogen or methyl, or R1 conjointly with R2 denotes tetramethylene and/or R4 conjoint-ly with R5 denotes tetramethylene, R2 denotes alkyl with 1 to 8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl with 1 to 8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, R6 denotes alkyl with 1 to 8 carbon atoms, R7 denotes alkyl with 1 to 8 carbon atoms or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene with 2 to 11 carbon atoms, and n denotes 0 or 1, is incorporated.
36. Process according to claim 34, characterized in that a compound of the formula I in which R1 and R5 independently of one another denote hydrogen or methyl, R2 denotes alkyl with 1-4 carbon atoms, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms, R6 denotes alkyl with 1 to 4 carbon atoms, R7 denotes alkyl with 1-4 carbon atoms or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene with 4 or 5 carbon atoms, and n denotes 0 or 1, is incorporated.
37. Process according to claim 34, characterized in that a compound of the formula I in which R1 denotes hydrogen or methyl, R2 denotes alkyl with 1-4 carbon atoms or conjointly with R1 denotes tetramethylene, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms or conjointly with R5 denotes tetramethylene, R5 denotes hydrogen, R6 denotes alkyl with 1 to 4 carbon atoms or phenyl, R7 denotes alkyl with 1 or 2 carbon atoms or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene with 5 carbon atoms and n denotes 1, is incorporated.
38. Process according to claim 34, characterized in that a compound of the formula I in which R1 denotes hydrogen or methyl, R2 denotes alkyl with 1-4 carbon atoms, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon atoms, R5 denotes hydrogen, R6 denotes alkyl with 1 to 4 carbon atoms, R7 denotes alkyl with 1 or 2 carbon atoms or the group in which R1 to R5 have the indicated meaning, or R7 conjointly with R6 denotes alkylene with 5 carbon atoms and n denotes 1, is incorporated.
39. Process according to claim 35, characterized in that a compound of the formula I in which n denotes the number 1, is incorporated.
40. Process according to claim 34, characterized in that the polymer is a polyolefine.
41. Process according to claim 40, characterized in that the polyolefine is polypropylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1065073A CH585685A5 (en) | 1973-07-20 | 1973-07-20 | Aldehyde-phenols useful as antioxidants of org. materials - prepd. from substd. benzyl dithiocarbamate and aldehyde |
| CH590874 | 1974-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048529A true CA1048529A (en) | 1979-02-13 |
Family
ID=25698626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA74204919A Expired CA1048529A (en) | 1973-07-20 | 1974-07-17 | Antioxidant hindered phenolaldehydes |
Country Status (14)
| Country | Link |
|---|---|
| JP (2) | JPS5044182A (en) |
| AT (1) | AT336575B (en) |
| AU (1) | AU7137874A (en) |
| BR (1) | BR7405954D0 (en) |
| CA (1) | CA1048529A (en) |
| DE (1) | DE2433050C2 (en) |
| DK (1) | DK392774A (en) |
| ES (1) | ES428400A1 (en) |
| FR (1) | FR2237870B1 (en) |
| GB (1) | GB1455766A (en) |
| IT (1) | IT1017311B (en) |
| LU (1) | LU70563A1 (en) |
| NL (1) | NL7409342A (en) |
| SE (1) | SE7407449L (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4317933A (en) * | 1974-01-22 | 1982-03-02 | The Goodyear Tire & Rubber Company | Preparation of antioxidants |
| JPS5522678A (en) * | 1979-06-06 | 1980-02-18 | Borg Warner | Hindered phenolaldehyde and its manufacture |
| US4284823A (en) * | 1979-10-15 | 1981-08-18 | The Goodyear Tire & Rubber Company | Process for preparing 3-(3,5-di-tert.alkyl-4-hydroxy-phenyl)-2,2-di-substituted propionaldehydes |
| JPS58147378U (en) * | 1982-03-30 | 1983-10-04 | 株式会社オ−デイオテクニカ | Microphone windshield screen |
| JPS60151426A (en) * | 1984-01-20 | 1985-08-09 | N S K Warner Kk | One-way clutch bearing |
| DE3729632A1 (en) * | 1987-09-04 | 1989-03-16 | Schaeffler Waelzlager Kg | FREE CLUTCH WITH CLAMP BODIES |
| DE4213750A1 (en) * | 1992-04-25 | 1993-10-28 | Basf Ag | Process for the preparation of 3- (hydroxyphenyl) propionaldehydes and optionally the production of 3- (hydroxyphenyl) propanols |
| CN1329586A (en) * | 1998-12-11 | 2002-01-02 | 日产化学工业株式会社 | Processes for preparation of (p-chlorophenyl) propanol derivatives |
-
1974
- 1974-06-06 SE SE7407449A patent/SE7407449L/xx not_active Application Discontinuation
- 1974-07-10 DE DE19742433050 patent/DE2433050C2/en not_active Expired
- 1974-07-10 NL NL7409342A patent/NL7409342A/en not_active Application Discontinuation
- 1974-07-17 CA CA74204919A patent/CA1048529A/en not_active Expired
- 1974-07-17 GB GB3163874A patent/GB1455766A/en not_active Expired
- 1974-07-18 AU AU71378/74A patent/AU7137874A/en not_active Expired
- 1974-07-18 BR BR595474A patent/BR7405954D0/en unknown
- 1974-07-18 LU LU70563A patent/LU70563A1/xx unknown
- 1974-07-19 IT IT2538674A patent/IT1017311B/en active
- 1974-07-19 FR FR7425178A patent/FR2237870B1/fr not_active Expired
- 1974-07-19 AT AT600874A patent/AT336575B/en active
- 1974-07-19 DK DK392774A patent/DK392774A/da unknown
- 1974-07-19 JP JP8314774A patent/JPS5044182A/ja active Pending
- 1974-07-19 ES ES428400A patent/ES428400A1/en not_active Expired
- 1974-10-15 JP JP11858274A patent/JPS5111726A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2237870B1 (en) | 1976-10-22 |
| AU7137874A (en) | 1976-01-22 |
| DE2433050C2 (en) | 1983-06-09 |
| FR2237870A1 (en) | 1975-02-14 |
| LU70563A1 (en) | 1976-05-31 |
| BR7405954D0 (en) | 1975-05-13 |
| GB1455766A (en) | 1976-11-17 |
| ES428400A1 (en) | 1976-09-16 |
| IT1017311B (en) | 1977-07-20 |
| NL7409342A (en) | 1975-01-22 |
| ATA600874A (en) | 1976-09-15 |
| AT336575B (en) | 1977-05-10 |
| JPS5111726A (en) | 1976-01-30 |
| DE2433050A1 (en) | 1975-02-06 |
| DK392774A (en) | 1975-03-10 |
| JPS5044182A (en) | 1975-04-21 |
| SE7407449L (en) | 1975-01-21 |
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