DE2321116A1 - PROCESS FOR THE PREPARATION OF HYDROXYDIPHENYL COMPOUNDS - Google Patents

Description

Patent attorneys

Dip! - Ing. P.W.rth

Dr. V. Schrnisd-Kowarzik

Dipl. Ing- G. D-wnenbarg

Dr. P. W & inhcU, Dr. D. Gudel

6 Frankfurt / M-, Gr. Eschenheimer Str. 39

SANDOZ AQ BASEL CSch weiz}

Case 150-3385

Process for the preparation of hydroxydiphenyl compounds

The invention relates to a method for manufacturing of hydroxydiphenyl compounds of the formula

N-CO-

(Y)

wherein R is a tertiary alkyl radical with 4-9 C-Aton.en, an alkyl, cycloalkyl or cycloalkylalkyl radical with 1-18 carbon atoms, an aralkyl radical with up to

309844/1176

to 18 carbon atoms,.

Ϊ .. hydrogen, an alkyl, cycloalkyl or Cycloalkylalkyl radical with 1-9 carbon atoms, halogen,

R ₁

CN, CP ,, \ L, COOMe, COOZ or'CONHZ, -> HO- ^ SV

(O
R ₂

Z is an alkyl radical with 1-9 carbon atoms, Me. Hydrogen, - Ni, Zn, Mn or Cu,

X .- hydrogen or the CO radical which is connected to Y to form a 5- or 6-membered ring,

Υ a saturated or unsaturated, p-valent, aliphatic, cycloaliphatic or araliphatic hydrocarbon radical with up to 22 carbon atoms and / or an optionally substituted aromatic radical with up to 22 carbon atoms, the radicals mentioned directly or via the intermediate member -COO - or -CONH- are bound to the radical in square brackets, and can be interrupted once or twice by sulfur or oxygen atoms or by -COO- or -CONH- and / or can carry halogen, OH, CN or COOH as substituents, η 1 or 2
m 1 or 2
ρ means 1, 2, 3 or 4,

309844/1176

and if n = 1 and p = 2 Y can also stand for the direct bond, which is characterized in that there is a connection the formula

(II)

with a compound of the formula

Y (COOH) _p (III)

where Y directly, via -00C- or -NH-CO- to the carboxyl group is bonded, or a functional derivative thereof, and when Me is a divalent cation, the resulting Converts compound into the corresponding salt. The invention also relates to those produced in this way Compounds of the general formula (I) and their use for stabilizing organic materials. The invention also relates to compounds of the formula (II) which are new and a process for their preparation. The connections of formula (II) are easily accessible from the corresponding nitro compounds by reduction. This reduction can easily be carried out according to generally known methods, e.g. according to Bechamp or

309844/1176

-4- Case 150-5385

by catalytic hydrogenation. The ones used as raw materials Some of the nitro compounds are known or can easily be prepared by generally known analogy processes will.

The radical R in formulas (I) and (II) can have the following meanings, for example: tert-butyl, 2-methyl-2-butyl, 2,3-dimethyl-2-butyl, 2-methyl-2-pentyl, 3-methyl-3-pentyl, 3-ethyl-3-pentyl, 2,4-dimethyl-2-pentyl, 2-methyl-2-hexyl, 3-methyl-3-hexyl, 3,4-dimethyl-3- hexyl, 3,5-dimethyl-3-hexyl, 2-methyl-2-heptyl, 3-methyl-3-heptyl, 4-methyl-4-heptyl, 2,3,4-trimethyl-3-pentyl, 2, 4,4-trimethyl-2-pentyl, 3-ethyl -3-heptyl, 2-methyl-2-octyl, 4-methyl-4-octyl. R ₁ can also have a ring structure, such as, for example, 1-methyl-cyclo: pentyl, 1-methyl-cyclohexyl, 1-methyl-cycloheptyl, 1-propylcyclopentyl and 1-butyl-cyclopentyl. R 1 preferably has 4 to 6 carbon atoms, in particular R 1 is tertiary butyl. The alkyl radical R ₂ in formulas (I) and (II) can be primary, secondary or tertiary, straight-chain or branched as desired. Examples of the radical R ₂ are: methyl, ethyl, propyl, butyl, pentyl, hexyl and the unbranched alkyl radicals with. 7 to 18 carbon atoms. Examples of secondary alkyl radicals are: isopropyl, 2-butyl, 3-methyl-2-butyl, 2-pentyl, 2,2-dimethyl -3-butyl, 2-kexyl, 3-hexyl, 2-methyl-3-pentyl, 3-methyl-2-

30984A / 1176

- 5 - Case 150-3385

pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-3-pentyl, 2,4-dimethyl-3-pentyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-methyl-3-. hexyl, 4-methyl-3-hexyl, 5-methyl-3-hexyl, 3-ethyl-4-hexyl, 2,2-dimethyl-3-hexyl, 2,4-dimethyl-3-hexyl ', 2,5-dimethyl-3-hexyl, 3,4-dimethyl-2-hexyl, 2-methyl-3-heptyl, 3-methyl-2-heptyl, 3-methyl-4-heptyl, 4-methyl-3-heptyl, 5 ~ methyl-3-heptyl, 6-methyl-2-heptyl, 2-octyl, 3-octyl, 4-octyl, 2,2,4-trimethyl-3-pentyl, 5-ethyl-2-heptyl, 2,2-dimethyl-3-heptyl, 2,6-dimethyl-4-heptyl, 2-methyl-3-octyl, 3-methyl-4-octyl, 6-ethyl-3-octyl, 2-decyl, 5-decyl, 2,2-diethyl-3-octyl, 2-methyl-4-nonyl, 3-methyl-4-nonyl, 6-ethyl-3-decyl, 7-ethyl-2-methyl-4-nonyl, 2-dodecyl, 2,6,8-trimethyl-4-nonyl, 2-tridecyl, 2-tetradecyl, 2-pentadecyl, 2-hexadecyl. Rp as Cycloalkyl radical can e.g. also be cyclopentyl, cyclohexyl, cycloheptyl, 2-, 3- or 4-methyl-cyclohexyl, cyclooctyl, 2,5-, 2,6-, 3 * 4- or 3> 5-diniethyl-cyclohexyl, l-cyclohexylpropyl, 2-propyl-cyclohexyl, 3,3,5-trimethyl-cyclohexyl, 2-butylcyclohexyl, 4-tert. Butyl-cyclohexyl, 3-methyl-6-isopropylcyclohexyl and be cyclododecyl.

Possible cycloalkylalkyl radicals for Rp are, for example, cyclohexyl-methyl, 2-cyclohexyl-ethyl, cycloheptyl-methyl / 3-cyclohexyl-propyl, cyclooctyl-methyl, cycloundecyl-methyl and cyclododecyl-methyl. In addition, R _? equal to R.

3 0 S 3 4 4/1 1 7 6

- 6 - Case I50-3385

or a branched radical such as, for example, 2-methyl-1-propyl, 2,2-dimethyl-1-propyl, 2-methyl-1-butyl, 2-ethyl-1-butyl, 2,2-dimethyl-1-butyl , 2-methyl-1-pentyl, 3-methyl-1-pentyl, Λ-methyl-1-pentyl, 2,4-dimethyl-1-pentyl, 2-ethyl-1-hexyl, 2,2-dimethyl-1 -hexyl, 2,2,4-trimethyl-1-pentyl, 4-methyl-2-propyl-1-pentyl, 3,7-dimethyl-1-oetyl, 2,2-dimethyl-1-decyl. If Rp is an aralkyl radical, this is preferably benzyl / phenylethyl. Preferably R _? one of the mentioned radicals with 4 to 9 carbon atoms, preferably identical to R, in particular tertiary butyl * The alkyl, cycloalkyl or cycloalkylaicyl radical R-. can be primary, secondary or tertiary, straight-chain or branched as desired. Such radicals with 1-9 carbon atoms have already been mentioned above for R ₁ and R 2. R-, but can also denote hydrogen, halogen such as bromine and in particular chlorine, CN, CF., or - COOK, COOZ or · -CONHZ, where for the alkyl radical Z those for R, and R _? .Called alkyl radicals with 1-9 carbon atoms. Z is preferably methyl or ethyl. R., is preferably hydrogen.

The amino groups in formula (II) are preferably in the ortho and para positions, based on the direct bond which connects the two benzene rings in formula (II) to one another. Furthermore preferred are those compounds of formula (II), ^/ in which only occurs an amino group, the. Ie those compounds of formula (II)

309844/117 6

Case 150-3385

where η is the number 1. As starting materials of the formula (II), where

tert. Butyl A = HO

tert. Butyl

are to be mentioned

NH,

NH,

NH,

NH,

A - / QV-COOH

NH,

Cl

The starting materials of the formula (III) are mono- or polycarboxylic acids, or their functional derivatives. Examples of monocarboxylic acids are: acetic acid, propionic acid, butyric acid, Valeric acid, caproic acid, caprylic acid and higher molecular weight straight-chain monocarboxylic acids with up to 2o carbon

309844/1176

Atoms of matter, for example stearic acid and araohic acid. The monocarboxylic acids can also have a branched carbon structure, examples of which are: isobutyric acid, isovaleric acid, 2-methylbutyric acid, pivalic acid, 2-ethylbutyric acid, 3i3-dimethylbutyric acid _, isocaproic acid, 2-methylnrvaleric acid, 2,2-dimethyl-n- valeric acid, 2-ethyl-caproic acid, 2 = ethyl ~ 2-methyl-caproic acid ", 2,2-dimethyl-caprylic acid and 2,2-D: '. inethy 1-undecanoic acid. • Suitable monocarboxylic acids are also those which instead of aliphatic ^ contain aromatic radicals or at the same time aromatic and aliphatic radicals, examples of which are: benzoic acid, o-, ni- and p-toluic acid, 2,3-, 2,4-, 2,5-, 3,4- and 35-diroethylbenzoic acid , 1- and 2-naphthoic acid, biphenyl-2- and biphenyl-4-carboxylic acid, phenylacetic acid, hydrocimic acid, 2-, 3- and 4-phenyl-butyric acid, monocarboxylic acid of the formula (III) in which the hydrocarbon radical Y is replaced by '0 - Or S atoms are interrupted, for example: methoxy-acetic acid, butoxy-acetic acid, 2-methoxy-benzoic acid , 4-ethoxy-benzoic acid, 2,3-, 2,4-, 2,6- and 3,5-dimethoxybenzoic acid, 2-methoxy-phenoxyacetic acid, 2-phenoxy-benzoic acid, methoxy-ethoxy-acetic acid, 4-ethoxy ethoxy-benzoic acid, dodecyl-thio-acetic acid, 2- (octadecylrr.ercapto) -propic acid, phenylmercapto-acetic acid and methylmercapto-ethoxyacetic acid. The monocarbon materials that can be used as starting materials

309844/1 176

- 9 - Case 150-3385

acids in the hydrocarbon residue can also form the bridges-COO- or -CO-NH- contain. Examples are: Adipic acid - inonomethyl ester, terephthalic acid monooctyl ester, Maleic acid monoester of 2,6-dichlorophenol, the Mono-anilide of diglycolic acid, the mono-butylamide of thiodiglycolic acid and the carboxylic acid of the formula

HOOC

OC ₂ H ₅

The radical Y in formulas (I) and (III) can be replaced by halogen, preferably be substituted by chlorine. The nitrile and hydroxyl groups in ' Question. The hydroxyl group is preferably phenolic (attached to a benzene ring) and sterically hindered by at least an ortho tertiary alkyl group. The starting materials of the formula (III) can also contain several carboxyl groups contain. Examples of such are: maleic acid, adipic acid, glutaric acid, methyl succinic acid, 2-methylglutaric acid, 3-methyl-glutaric acid, meso-2,3-dimethyl-succinic acid, 2-ethyl-2-methyl-succinic acid, 2,2-dimethyl-glutaric acid, 2,4-dimethyl-glutaric acid (sym.), 3,3-dimethyl

309844/1176

- Io - Case I50-J5385

glutaric acid, pimelic acid, j5-ethyl-3 ~ methyl-glutaric acid, 2,5-dimethyl-adipic acid, Suberic acid, azelaic acid, dipropylmaionic acid, 3-tert-butyl-adipic acid, sorbic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, Cyclohexane-1,1-diacetic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, diglycolic acid, thiodiglycolic acid, Phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, Tetraehlorphthalic acid, 1,8-naphthalene-dicarboxylic acid, Phenylsuccinic acid, diphenyl-2,2-dicarboxylic acid, benzene-1,2,3-, 1,2,4- or -1,3,5-tricarboxylic acids 1,2,3-propane-tricarboxylic acid, 1,3,5-pentane-tricarboxylic acid, pyromellitic acid and Naphthalene-l ^^ jS-tetracarboxylic acid.

Preferred radicals for Y are, for example, monovalent radicals such as:

-CH, -CH ₂ -CH ₂ -COOK

tert. -

o ^H iω -CH ₀ -CH ₀ -COONi

9 19. 2 2g

nC ,, H ₀₇ -CH = CH-CH = CH-CH,

13 27 3

11-C ₁₇ H ₃₅ -CH ₂ -CH _2- C (CH ₃ ) (C ₆ K ₄ OK) ₂

ⁿ " ^c l8 ^H 37

309844 / 11.76

Case I50-33S5

-, CH ₂ Cl
-CH ₂ CH ₂ Cl '

-CH ₂ -CH ₂ -COOCH ^

in addition are suitable:

C ₂ H ₅

COOH

OC ₂ H ₅

OH

CH-

CH,

NS.

309844/1176

Case 150-3385

i-3-C

-. qHoc

In addition, polyvalent radicals are suitable, such as e.g.

COOH

-CH ₂ -CH ₂ -

-CH ₂ -CH ₂ -S-CH ₂ -CH ₂ (-CH ₂ -CH ₂ -COO-CH ₂ ) ₄

COOCgH ₁₇ (I)

Mention should be made of the compounds of the formula

309844/1 176

NH-CC

-Y P

Case 150-3385

(Ia)

wherein ρ, R ₁ , R ₂ , R and Y have the above meanings. The nitrogen atom bound to dr.ri benzene ring is preferably in the ortho or para position to the diphenyl bond. Mention should also be made of the compounds of the formula

R-

O) - (O

M-CO-Y

(Ib)

NH-CO-Y

wherein R 1, Rp, R, and Y have the meanings mentioned above and Y represents a monovalent radical.

Within the compounds of the formula (I) there are also compounds the formula

(Ic)

309844/1176

. - 14 - Case I50-5385

where R., R _? , R, and η have the above meanings, and Y represents a divalent radical.

Within the compounds of the formula (I) there are also compounds the formula

wherein R 1, Rp, R 1, X and Y have the above meaning and Y represents a trivalent or tetravalent radical.

The radical Y can be added to the written CO of the formula (Ia), (Ib), (Ic) and (Id), as mentioned, directly or via a of the groups -COO-, -CONH- be bound, so that the

ü ° de ^ υ ii -C-Y -C-C-O-Y

result in the following bindings: _(l or \\ \\ and

0 0

i! if

-C-C-NH-Y *

The process according to the invention, i.e. the conversion of the starting materials of the formula (II) and (II) to end products of the ■ Formula (I) is an acylation. This analogy reaction can be carried out by generally known methods. if the carboxylic acid of the formula (III) is sufficiently non-volatile, e.g. stearic acid, adipic acid or terephthalic acid, can be used heat the two starting materials together, the desired end product being formed with elimination of water. One can

309844/1176

- 15 -. Case I50-5385

in the melt at temperatures of approx. 12o-22o °, below ·. normal or reduced pressure, or using inert solvents, such as xylene, for example, this being slowly distilled off during the reaction and serving as an entrainer to remove the water that is split off. Catalysts such as boric acid can be used to accelerate the reaction. The reaction of the amine with the carboxylic acid can also be carried out under milder conditions if the reagents customary in peptide chemistry, such as, for example, biscyclohexylcarbodiimide, are used. Functional derivatives of the carboxylic acids of the formula (III) are their anhydrides, such as, for example, succinic anhydride, phthalic anhydride, homophthalic anhydride, the anhydride of diglycolic acid and that of thiodiglycolic acid. The acylation can also be carried out very well with the chlorides of the acids of the formula (III), preferably with the use of acid-binding agents. If one starts out from compounds of the formula (III) in which 'ρ is greater than 1, only one of the carboxyl groups in the polycarboxylic acid can be used for the acylation reaction, so that the remaining carboxyl groups remain free and the remainder in the end product of the formula (I) Y appear as a substituent; but you can also choose the reaction conditions and the ratio of the two starting materials

309844/1176

'-' - 16 - Case 150-3385

choose so that all the carboxyl groups of the starting materials of the formula (III) take part in the acylation reaction, so that the Y radical in the end product of the formula. (I) no carboxyl group as Contains substituents. In order to get ingredients of formula * (I) get, in which X means the CO radical, which is connected with Y to a 5- or 6-membered ring, you have to go from corresponding polycarboxylic acids or their suitable functional derivatives. All are suitable for this Polycarboxylic acids which are 5 or 6-membered cyclic imides can form, such as maleic anhydride, succinic acid, glutaric anhydride, phthalic anhydride, homo-. phthalic acid, tricarbalylic acid, benzene-1,2,3- or -1,2,4-tricarboxylic acid and pyromellitic acid.

In these cases, Y is linked directly to the remainder in the square brackets of the formula (i). The connections in which Y via the intermediate link-COO- to the rest in the square Bracket is bound, as they come under the compounds of formula (Ia) and (Ib) are also obtained by that a compound of formula II with oxalic acid or a functional derivative thereof reacts and the product obtained with an organic amine of the formula

Y (NH ₂ ) P (IV)

where Y and ρ have the meaning given above.

30 9 8 44/1 176

Case 150-3385

How to bring a compound of formula (II) with a Esters of oxalic acid for the reaction, an amino group of the compound of the formula (II) being reacted with one mole of oxalic ester leaves. Such reactions proceed smoothly when the mixed reactants are heated with elimination of one Mols of alcohol from one mole of the oxalate used. Low molecular weight oxal esters, such as diethyl oxalate and the dimethyl oxalate are special for this reaction suitable »From such amide esters of oxalic acid one can through Reaction with organic amines substituted diamides of oxalic acid win i.e. compounds of the formula (I) in which Y via the intermediate -CO-NH * to the remainder in the is tied in square brackets:

R,

N-CO-COO-Alkyi \ H / n

N-CO-CO-NH-Y \

The latter oxalic acid diamides can also be used according to the invention can be made by making an ester amide of oxalic acid

309844/1176

Case 150-3385

the formula

Alkyl-OOC-CO-NY ~.

I H

(V)

with a compound of the formula (II). This analogy ' reaction takes place easily when one of the two reactants mixed and heated together until the elimination of alcohol ends is. Per amino group in the compound of formula (II) is reacted with one mole of a compound of the formula (IV). As can be seen from the introduction to this section, Y in the compounds of formula (I) and (III) also for the direct bond, provided that η 1 and ρ 2 mean. The connections so defined are symmetrical Oxamides of the formula ί

N-CO-CO-W-H H

Such compounds are easily obtained from one mole of one functional derivative of oxalic acid, such as a low molecular weight Esters or of oxalyl chloride, by reaction with two moles of an amine of the formula (II), in which η for the Number 1 stands. This analogy procedure runs very smoothly

309844/1 176

- 19 - Case 150-3385

and 'is well known.

The remainder R ,. in the formula (I) the carboxyl group can mean In addition, the radical Y can also be replaced by carboxyl groups, be substituted. These carboxyl groups can be in free form or in the form of salts of nickel, zinc, Manganese or copper. Such salts can easily be prepared by customary methods. The preferred manufacturing method is in that you have a soluble salt of the carboxylic acids in question, in particular an alkali salt, dissolved in Viasser or in organic solvents, with a soluble salt of nickel, zinc, manganese or copper. Through double implementation the desired heavy metal salt of the formula (I) is formed from the soluble reactants. The latter are usually sparingly soluble and can easily be isolated in pure form by filtration and washing. The invention also relates to the use of the new compounds of the formula (I) as stabilizers. To this end the new compounds are incorporated into substances sensitive to light, oxygen and heat or as a protective layer applied to the substances to be protected. Thanks to their stabilizing effect, those used in this way preserve new compounds protect sensitive substances from destruction. The possible applications in the plastics sector are particularly numerous. It is used, for example, in the following

309844/1176

- 2ο - Case 15ο-3385

Plastics in question: cellulose acetate, cellulose acetobutyrate, polyethylene, polypropylene, polyvinyl chloride acetate, polyamides, Polyurethanes, polystyrene, ethyl cellulose, cellulose nitrate, polyvinyl alcohol, polycarbonates, silicone rubber, cellulose propionate, Melamine-formaldehyde resins, urea-formaldehyde resins, Allyl casting resins, polymethyl methacrylate, polyester and polyacrylonitrile, and corresponding copolymers, such as Acrylonitrile-butadiene-styrene copolymers. Natural substances can also be stabilized, such as rubber or Cellulose. The substances to be protected can be in the form of plates, rods, coatings, foils, films, tapes, fibers, Granules, powders and other processing forms, or in the form of solutions, emulsions or dispersions. The incorporation or coating of the materials to be protected takes place according to methods known per se. A particularly important application method consists in the intimate Mixing of a plastic, for example polypropylene in granulate form, with the new compounds, e.g. in one Kneader, and in the subsequent extrusion. In this way you get a very homogeneous mixture, what a thing good protection is important. When extruding, for example, films, tubes or threads are obtained. The latter can become textiles be interwoven. In this mode of operation, the stabilizer is incorporated into a textile material before processing

309844/1176

- 21 - Case I50-3385

mixed with the polypropylene.

Plastics do not necessarily have to be polymerized or be condensed 'before mixing with the new compounds he follows. You can also mix monomers or prepolymers or precondensates with the new stabilizers and only afterwards convert the plastic into its final form by condensing or polymerizing. The new stabilizers can not only be used to stabilize clear films, plastics and the like, they can also be used in opaque, semi-opaque or translucent materials and their surface for degradation by ultra-violet light, air and heat is sensitive. Examples of such materials are: foamed plastics, opaque films and coatings, opaque papers, clear and opaque colored plastics, fluorescent pigments, polishes for automobiles and furniture, creams and lotions and the like, whether they are opaque, clear or translucent are.

The process described above allows the synthesis of very different variants of compounds of the formula (I), so that the constitution can be designed in such a way that the stabilizing effect in certain plastics is particularly good is high. For example, consider the relationship between

309844/1178

Constitution of compounds of the formula (I) "and their action mentions that the "stabilizing" effect in polyalkylenes, especially in polypropylene, it is especially good if the molecule is made up of a substantial proportion of saturated aliphatic Groups. The protective effect of the new compounds against light, especially against ultra-violet Light is particularly high when the carboxylic acids of the formula (I) are used in the form of the nickel salts, in particular in polyalkylenes. For stabilization against UV light from The manganese and copper salts are particularly suitable for polyamides. Very good light stabilizers are also those representatives of the general formula (I), which have the oxamide structure « These oxamides can be symmetrical or asymmetrical. When the oxamide structure and the heavy metal carboxylate groups absent in the compounds of formula (I) is the photoprotective effect not particularly pronounced, in certain cases it can even be almost entirely absent. Such compounds of formula (I) however, they are very good stabilizers against the decomposing ones Effects of oxygen (air) and heat. This effect is due to the sterically hindered phenolic hydroxyl group. This effect of sterically hindered hydroxyl groups is well known, for example 2,6-di-tert-butyl-pcresol much used as an antl-oxidant. However, these and similar compounds have the disadvantage that they are relatively

309844/1176

- 23 - Case I50-33S5

are volatile and therefore when incorporated into high polymers at higher temperatures, or also during long storage or Sublimate away from the organic materials to be protected during use. If in 2,6-di-tert-butyl-p-cresol the If the methyl group is replaced by the phenyl radical, the volatility is greatly reduced; but it is still closed large, and also the effectiveness as an anti, Oxydans lower. The further enlargement of the molecule naturally brings an even greater reduction in the Volatility. It has been shown that the enlargement of the molecule cannot be achieved in any way, in order to get good stabilizers. The newly introduced molecular components have to give the end products very specific ones Properties such as good compatibility in the organic materials to be protected and high inherent stability of the active ingredients. The present invention also relates to the materials used to stabilize compounds of the Formula (I) included. As shown in some examples above, the incorporation of the new compounds into the to protective materials in any processing stage according to aich

30984Λ / 1176

- 2h - case

known methods take place, the amount of incorporated protective agents can vary within wide limits, ζ, Β. between 0.01 and 5 %, preferably between 0.05 to 1 %, based on the materials to be protected; The stabilized organic materials can only contain compounds of the formula (I) or, in addition, other auxiliaries for improving the properties. Such aids are, for example: UV absorbers and stabilizers against destruction by heat and oxygen. Of the latter, especially those that belong to many classes of substances other than the compounds of the formula (I), such as, for example, organic compounds of sulfur, tin and phosphorus, 2-hydroxy-benzophenones and hydroxybenzotriazoles. With such mixtures of stabilizers, the stabilizing effect is often particularly high, because there is a synergistic effect.

In the following examples, F is the melting point, the parts are parts by weight and the percentages are percentages by weight Temperatures are given in degrees Celsius. The chemical constitution of all compounds listed in the examples is proven microanalytically and partly by spectral analysis.

3 0 9 8-4 V 11 7 6

Case 150-2285 ,,.

Examples of the preparation of end products of the formula (I).

example 1

tert

NH-CO-C ₁₇ H ₃₅ Cn)

tert.C ₄ H _g

29.7 parts of 3,5-di-tert-butyl-4-hydroxy-2'-aminobiphenyl are dissolved in 8.4 parts of pyridine and 40 parts of toluene in a nitrogen atmosphere with exclusion of moisture. A mixture of 51.8 parts of stearic acid chloride and 60 parts of toluene is then slowly added. The mixture is heated under reflux for one hour, cooled and the solution is extracted with water. The toluene is removed from the organic phase by distilling off in vacuo. After recrystallization of the distillation residue from ethanol, 54.2 parts of the new compound are obtained in the form of colorless crystals.

Example 2

C (CH _x )

yi>

44/1176

- 26 - Case. 15ο-3385

Dissolve 9.0 parts of Di-tert-butyl-J 5.5-hydroxy-4-4- ¹ -aminobiphenyl in loo parts of toluene and simultaneously under stirring at 5 °-lo 3.1 parts of triethylamine and 6.1 parts of 4 -Tert. 'Butyl benzoyl chloride is allowed to react for 6 hours at 2o-3o ° and the precipitated salt is filtered off. The Τοίμοί is removed from the piltrate by distillation in vacuo, whereupon the pure compound in the form of colorless crystals is obtained from the residue after recrystallization from acetone-water.

Example 3

tert.-

29.7 parts of 3,5-di-tert-butyl-4-hydroxy-4'-aminobiphenyl dissolves .man with stirring in 40 parts of toluene and 8.4 parts of pyridine. As described above in example 1, you set with 41 parts n-Dodecylthiopropionic acid chloride, dissolved in όο parts of toluene, around. The new compound is obtained after recrystallization from hexane in the form of colorless crystals.

Example 4 tert.

Nh-CO-CH ₂ CH ₂ COOH

tert-C ₄ H ₉

309844/1 176

- 27 - Case I50-3385

5 parts of succinic anhydride are stirred in 120 parts of benzene at 70 ° with exclusion of moisture and a solution of 14.8 parts of 3j5-di-tert-butyl-4-hydroxy-4'-aminobiphenyl in 24 parts of benzene is added. After a short time, the reaction product begins to separate out in the form of needle-shaped crystals. The reaction is complete after 1 to 2 hours at ¹ yo. It is allowed to cool slowly to 10 ° to 15 ° and the colorless needles are filtered off. After washing with a little benzene petroleum ether 1: 1, the pure compound is obtained in the form of colorless needles.

Example 5

NH-C-C-IIH

tert. Cj ^ Hq

22.3 parts of oxalic acid monoethyl ester (2-ethyl) anilide, 3o.2 parts of 3,5-di-tert-butyl-4-hydroxy-2'-aminodiphenyl and 1.1 parts of boric acid are added for 3 hours stirred at 150 ^0. The alcohol formed is distilled off in vacuo. To work up the reaction mixture, approx. 30 parts of glacial acetic acid are run into the warm mass and the mixture is stirred at 100 ° until the original settlement product has completely dissolved. Then one drops the re-

309844/1176

- 28 - Case I50-3385

action product from the solution again. The pulpy mass stir until completely homogeneous. After looking at the grooves it is washed with water until the filtrate is colorless and the residue no longer smells of glacial acetic acid. To clean it, stir again well with alcohol, nutseth and dries in the vacuum drying cabinet. A colorless, crystalline product with a melting point of 174-176 ° is obtained.

example 6- tert • ^C 4 ^H 9 NH- O HO - / F ^ > -i C ₁₇ H I! ) - '
tert.C 4 ^H 9 'N 35 ~ n \ - ι;
O

With exclusion of moisture, 15.6 parts of 3 * 5-tert-butyl-4-hydroxy-2 ¹ , 4'-diamino-diphenyl are dissolved in 150 parts of toluene, the mixture is stirred over 10 and 11 parts of triethylamine and are slowly added at the same time 31 * 8 parts of stearic acid chloride. The reaction is allowed to complete at 40 for 5 hours, the precipitated salt is filtered off, the filtrate is evaporated in vacuo and the residue is crystallized twice from acetone. The new compound is obtained in the form of gray crystals.

The compounds in Tables 1 to 6 below are prepared in a manner analogous to that of the compounds of Examples 1 to 6

309844/1176

Case 150-3385

Table 1

(H ₅ C) ₃ C

IJH-CO -τ- Υ 'P

No. Y P. 1
(Example 1) C ₁₇ H ₃₅ (H) 1 2 C ₉ H ₁₉ (Ii) 1 3 C ₁₁ H ₂₃ (H) ' 1 CH 1 5 h (^> - c (ch ₃ ) _3. ' 1 6th ^H 2
C-CH
<> h
pH-CHp
HOOC 1 7th HOOC 1 8th -CH ₂ CH ₂ -SC ₁₂ H ₂₅ (n) . 1 9 - (CH ₂ ) ₄ - 2 Io -CHpCH ₀ -S-CH ₀ CH ₀ - 2

0 9 8 4 4/1176

Case 150-3335

Table 2

(H ₃ O) ₃ C
(H, C), C-. N-CO
3 '3 ι \
CO Y Kr. Y 11 "^ CH s ^ CH
II! ■ ■
/ CH ^ _C / CH
H ₂ 12th

309 8 44/1176

Case 150-338

e 150-3385

232111b

Table 3

(H ₃ C) ₅ C
ho - (q \ - / qV-nh-co- -
(H ₃ C) ₅ CI '-CH3 -Y.
) No. Y -C ₉ H ₁₉ I.
P. 13th -C ₁₁ H ₂₅ 1 14th " ^C 17 ^H 35 1 15th 1 16 -CH ₅ CH ₉ -COO-CH 1 17th
Example 2 -CHg-Cl 1 18th -CHgCHg-Cl • 1 19th -CHgCHg-S-C- ^ gHg ^ 1 2o -CHgCHg-COOH 1 21
Example 3 1 22nd
Example 4 1

309844/1 176

ORIGINAL

Table 3 (cont. I)

Case 150-3385

ι
No. -CHgCHg-COOg ^ P. 23 -CHgCHg-COOp 1 24 - (CH ₂ ) ^ . 1 25th -CHgCHg-S-CHgCHg- 2 26th ^ CH ₂ CHg-COO-CHg) ₄ C 2 27 -CH = CH-CH = ^ H-CH-J. 4th 28 ^ CHg) ₁₂ CH ₃ 1 29 4CHg) ₂₀ CH ₃ 1 3o -C (CH ^) ₃ 1 31 - (CHg) ₃ COOH 1 32 -CH = CH-COOH 1 33 - @ 1 34 1 35 1

30 9844/1178

Case I50-3385

Table 3 (cont. II)

No. Y OCH- ^ OCH ^ P. 36 1 37 . CH ₂ -CH ₂ -C (CH ₃ ) (C ₆ H ₄ OH (P)) ₂ 1 38 2 39 1

309844/1176

Case 150-3385

Tabel

H ₂

CH "CH

CH CH

H ₂

COOH

CH ₂ -CH ₂

30 98 44/1178

Case 150-3385

Tabel

(H ₃ C) 3 ^C - ^ 0> - ^R1 ₃ HO-- NH-CO-CONH-Y (H ₃ C)

R '.

33

(η)

- CK-

-COOH

-Cl

309844/1176

Case I50-3385

Table '6

(H ₃ C) ^ C
HO

- (O- Wi-CO-CO-NH-Y

(H ₃ C) ₃ C

37

(η)

OH

CH.

CH

309844/1176

Case 150-3385

Table 6 (continued)

NS

■ χ

n> -ococ ₂ H ₄ -sc ₁₂ H ₂₅

309844/1176

Case 150-33.85

Table '7

No.

(H, C), G.

qY-nh-go-y

ΙΊΗ-CO-Y

βκ

65 Example 6

61

The following connections are also made in the same way manufacturable:

No. 68

QV-NHCOC ₁₇ H ₃₅

SeCC ₄ H ₉

SeCC ₄ H ₉

SeCC ₄ H ₉

309844/1178

Case 150-3385

HO

tert.Cj t ^H 9 OH .OC ₂ H ₅ tert. C ₄ H ₉ <
/ "'A / V- tert.C ρ
/ 4 ^ 9 NH-CO-CO-NK- tert. C ₄ H ₉

No. 71

tert.

ζ ore

NH-CO-CO-NH

NH-CO-CO-NII

OC ₂ H ₅

No. 72

tert.

'- NH-CO-CO-NIi-C ₁₀ H _0n :

tert. C ₄ H ₉ 12 25

No. 73

COOH

NH-CO-CK

309844/1

- 4ο -

Case 15ο-33ί

No. 74

No. 75

(H ₃ C) ₃

Q \ _ NH-CO-C ₁₇ H ₃₅

QV-NH-CO-CO-NH- / Q

C (CH-)

C (CH ₃ J ₃

Examples of the use of the compounds of the formula (I) .

Example a

Powdery polypropylene is mixed uniformly with 0.4 % of compound no. 16 (see Table 4 above). After kneading for 5 minutes on a roller mill at 180, it is pressed into a sheet 1 mm thick. To test against oxidative degradation, disks 18 mm in diameter are punched out of these plates and, after the air has been displaced, they are stored in a closed system under oxygen. Kan is then heated to 190 , with an overpressure of about 20 mm Hg.

3098U / 1176

'- 41 - Case 150-3385

The oxidation of the plastic results in a pressure drop. The speed of this pressure drop is small, when the effectiveness of the stabilizer is high. One eats the time until the overpressure drops to 0.

Example b

Polypropylene (powder) is evenly mixed with 0.4% of the stabilizer to be tested. After working through for 5 minutes on a roller mill at 180 °, sheets 1 mm thick are pressed. To test the resistance to aging, an accelerated aging test is carried out at I4o in an air circulation furnace.

309844/1176

Claims (1)

Patent claims '1 \ method for producing hydroxydiphenyl comparison bonds of the formula (D wherein R is a tertiary alkyl radical with 4-9 carbon atoms, R_ an alkyl, cycloalkyl or cycloalkylalkyl radical with 1-18 carbon atoms, an aralkyir radical with up to 18 carbon atoms,
R, hydrogen, an alkyl, cycloalkyl or cycloalkylalkyl radical with 1-9 carbon atoms, halogen, R ₁ '·' ■ - ■ CN, CP ,, vL COOMe, COOZ or CONHZ, 3 HO ^ Z is an alkyl radical with 1-9 carbon atoms, and Me, hydrogen, Ni, Zu, Mn or Cu X is hydrogen or the CO radical that forms a 5- or 6-membered ring is connected, Y is a saturated or unsaturated, p-valent, aliphatic, cycloaliphatic or araliphatic Hydrocarbon residue with up to
309844/1 176 - 43 -. Case 150-3285 to 22 carbon atoms and / or an optionally substituted aromatic radical with up to 22 carbon atoms, the radicals mentioned being bonded to the radical in square brackets directly or via the intermediate member -COO- or -COMi-, and- a - or be interrupted twice by sulfur or oxygen atoms or by -COO- or -COKTH- and / or can carry halogen, OH, CN or COOH as substituents,
η 1 or 2
m 1 or 2 ρ means 1, 2, 3 or 4, and if n = 1 and p = 2 Y can also stand for the direct bond, characterized in that a connection the formula (II) (* ₂ > _n with a compound of the formula 309844/1176 Case 150-33B5 Y (COOH), wherein Y is bonded to the carboxyl group directly, via -OOC- or -NH-COr, or _{converts a functional derivative thereof 3} , and if Z is a divalent cation, converts the compound obtained into the corresponding salt. 2. The method according to claim 1, characterized in that compounds of the formula NH-CO (Ia) manufactures, where R ,, Rp, R ,, ρ and y. the meaning according to claim 1 to have . The method according to claim 1, characterized in that one Compounds of the formula 309844/1176 Case I50-33Ö5 (Ib) manufactures, wherein R,, R ", R., and Y have the meaning according to claim 1 to have. 4. The method according to claim 1, characterized in that one compounds of the formula D-, (Ic) manufactures, viorin R ,, Rp, R- ,, η and γ have the meaning according to claim 1 have. 5. The method according to claim 1, characterized in that one Compounds of the formula 309844/1176 Case .150-5385. R ₁ manufactures,
where R ,,
to have. R- ,, X and Y have the meaning according to claim Process for the preparation of compounds of the formula (Ia) and (Ib), characterized in that one Reacts compound of formula (II) with oxalic acid or a functional derivative thereof and the product obtained with an organic amine of the formula Y <NH ₂ ) _p (IV) where Y and ρ have the meaning given above. 7. Compounds of the formula (I) according to claim 1 8. Compounds of the formula (Ia) according to claim 2. 9. Compounds of Forir.el (Ib) according to claim J. 309844/1176 Case 150-3585. lo. Compound of formula (Ic) according to claim ¹ I, 11. Compounds of the formula (Id) according to claim 5 (II), Ita
the formula marked ψ ' The compounds of the formula tert. KO NK-CO-C tert. received on Einoabe LJbL- 309844/1176 Case 150-3385 ' The compounds of the formula tert. Cj ₊ H -NH-CO Q) - tert. The compounds of the formula HO- QV NH-CO-CH The .compounds of the formula tert. NH-Co-CH ₂ -CH ₂ -COOH tert. C ₄ H ₉ The compounds of the formula tert. C ^ Hq KO-Tf )) / QVnH-CO-CO-NH-ZQ ' feert. C ₄ K _g ^C 2 ^H 5 09844/1176 Case The compounds of the formula tert. tert. . The compounds of the formula tert. tert. - NH-CO-CO-NH-Z (A)) OCOCH ₂ -SC ₁₂ H ₂₅ wherein the substituent on ring A is ortho-, or para position is located. Compounds of the formula tert. NH-CO-CO-NH 0-COC ₂ H ₄ -SC ₁₂ K ₂₅ wherein the substituent on ring A is in ortho-, meta- or para position. 309844/1176 - 5ο - Case Use of compounds of the formula (I), (Ia), (Ib) , (Ic) and (Id) for stabilizing organic materials. . . Organic materials which contain compounds of the formula (i) as stabilizers. Organic materials that act as stabilizers compounds of the formula (I) and other stabilizers and costabills against the action of oxygen, Contain heat and light. The patent attorney: 309844/1178