DE2344525A1 - 1,5-DI (3 ', 5'-DIHYDROCARBYL-4'HYDROXYPHENYL) PENTYL DISCOUNTS - Google Patents

Description

PATENT ANWALTSBORO TlEDTKE - BüHLING '\ * / * KlNNE

TEL (0611) UKWH TELEX S24S45 tlpit CABLE ADDRESS German, apalenl Munich

8000 Munich

Bavariarlng 4

P.O. Box 202403 September 4, 1973

1.

Uniroyal, Inc., New York, New York 1UÜ2U, UGA

1,5-Di (V, V-dihyclrocarbyl- ^ '-hydroxyphenyl) pentyl-abbreviation

The invention relates to a neuro of compounds in general ^ ¹ Ii formula

HO - / HO - (

Λ -CH -

- CHR '

—Ι η

40981 1/1231

BATH ORIGINAL

K and K ¹ occupy H or an alkyl group; a with up to Λ carbon atoms and can either be untorrhindly or be part of a carbocyclic ring with S to 7 carbon atoms, including the carbon atom bearing the substituent A

R ² , R ⁵ , R ⁴ around! R ' are H ₁ alkyl, cycloalkyl, aryl, aralkyl and alkryl groups with up to 12 carbon atoms and can be the same or different no, where, if A has the meaning of -OH or = 0, R and R ¹ only hydrogen or alkyl and at least two

2 ^c )

R to R 'denote hydrocarbyl groups with at least 3 carbon atoms.

A is defined as -OH, -OR ⁶ , -GlV, = 0, = 11, = NR ⁷ , PO, =, PO. =, 0 0 0 °

RCO-, R ° -N-ir, OC-R ^ -CO or R ^ -NR ^ -NR ^f , where R ° is H, alkyl (C ₁ -C ₅₀ ), cycloalkyl (C ₅ -C ₇ ), Aryl, aralkyl, alkaryl, hydroxyalkyl, alkoxyalkyl, alkylaminoalkyl or alkylthioalkyl, the last seven radicals each having up to 16 carbon atoms.

7 ' ⁿ . " ^P - C 8 6

R denotes R ^J , R "-C- or R'-Sg ^ j, where R is defined in the same way as R. R and R can be the same or different. R ^tJ and R 'together with the N, an de: n rie hang in R -NR, form a heterocycliscxi en Hin ^.

R ^ means Al> ylon, oxydialkylene, thiodine inlkylor. or arylene with jev / eils bir. to 16 carbon atoms, vx irt 1, if A with a single bond; to de: a the same pentyl carbon atom is attached, and m is zero if A: a is attached to the same pentyl carbon atom with a double bond, η is an integer corresponding to the valence

8AD ORIGINAL

409811/1231

ability of A, ωwith the exception that η = 1, if A is bound by a double bond πη the same pentyl carbon atom.

In UC-I ¹ G 3 594 424, R-Krueger discloses compounds of the formula I in which R and H ^{1 form} a five- or six-membered ring and A is a ketone oxygen ir-t.

DT-OC 2 009 504 (BASF) ict discloses a number of compounds of the formula I in which R and H ^{1 are} hydrogen or together are an cycloalkyl group and A is a hydroxyl group, a ketone oxygen, a cyclic acetal or a cyclic group Mean thioacetal group.

The only other publication of compounds of the formula I is a publication by II. Wittmann, Monatshefte ^ 4_ 686-93 (1963). In the compounds disclosed, H and R 'denote hydrogen, and R to R- ⁷ denote hydrogen or CH1, and A is a ketone oxygen or a hydroxy group.

The compounds of formula I are prepared by condensation of 3,! /> - üialkyl-4-hydroxybenzaldehyde / represented by the method of G.II. Coppinger and TW Campbell, J. Am. Chem. Soc. 2Ü2-734-V36 (195317 with various ketones according to the description of Wittmann / Monatshefte 94_, 636-93 (1963X7 and DT-OS 2 009 ^r ^ 04 and also in ORGAIiIC HEACTIONS, Volume 16. The solvents used in the condensations were

BAD OR! G? Wäi 1/12 3 1 ^L

Alcohols. A generalized equation for this reaction is:

H V \ H H H

-C = O + HO - (\ /) -C-O + R-C-C-C-R '

^H Ö ^H

HR R ¹ H
-CCCC = C- (X /) -OH + 2HpO

The catalyst for the reaction is formal hydrogen chloride. It is used in a saturated alcoholic solution.

The resulting penradienone is then catalytically reduced with hydrogen and with a leveled catalyst to the pentanol-3 or pentanone-5 / R. Gornubert and HG Eckert, Bull. Goc. Chim. France 19Γ-Λ , 522-3 (195 ^ 17. Alternatively, the I'entadienone can be converted into the saturated ketone, and the latter is then in accordance with DT-OS 2 009 ^Γ Ό4 or by other known methods for the reduction of a Ketones can be reduced to an alcohol.

The l-'entanol-3 is then with an equiraolar amount of a Acid, a acid chloride or an acid anhydride in one Hydrocarbon or a chlorinated hydrocarbon as

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Solvent at temperatures from 20 to 14ü ° C reacted to to get the 3-Ientylertor. To win lolyester you can polybasic acids are used.

The preparation of the amides consists first of all in the catalytic reductive alkylation of 3-pentanone with ammonia or an amine in an alcohol. The new 3-pentylamine was then reacted with an equimolar amount of an acid, an acid chloride or an acid anhydride in a hydrocarbon or chlorinated hydrocarbon as solvent at temperatures from 20 to 140 ^° C. to give the desired amide. Polybasic acids can be used to produce polyamides.

Those useful in practicing this invention Acids, acid hydrides or acid chlorides are among others Formic acid, acetic acid, propionic acid, butyric acid, hexanoic acid, DecansMure, lauric acid, stearic acid, benzoic acid, Phenylacetic acid, oxalic acid, succinic acid, adipic acid, phthalic acid, terephthalic acid, toluic acid, salicylic acid, Phosphorus trichloride and phosphorus oxychloride.

Suitable amines used in reductive alkylation are ammonia, methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, cec-butylamine, ieobutylamine, t-butylamine, n-pentylamine, inopentylamine, n-IIexylamine, n-octylamine,

409811/1231 ^ß AD o _R i _GiNAL

23U525

n-dodecylarain, n-octadecylamine, cyclopentylamine, cyclohexylamine, Athyldinuin, propylenediamine, hexamethylenediamine, aniline, Benzylin and 2-aminoethanol.

The solvents which can be used in the preparation of the compounds according to the invention include methanol, ethanol, Isopropanol, H >> xar ,, cyclohexnn, benzene, toluene, xylene, Chloroform, carbon tetrachlorio "and dichloroethane.

The catalysts suitable for the required reductions are 1 ^! indium on carbon, 1 latin on carbon, Nickel on Kion ^ lguhr and lianoy-Nickol.

The chemical compounds according to the invention can be used as stabilizers, protective agents and antioxidants for organic substances (e.g. polymer, animal, mineral or vegetable oils, fish oil, fats, gasoline, etc.) which deteriorate when exposed to influences such as air, heat and light Experienced. Gie are particularly effective in connection with dialkyl-5, J'-thiodipropionates, for example dilauryl-3,5 ¹ -thiodipropionate. The present chemicals as antioxidants stabilize hydrocarbon chain polymers, including polyolefins (e.g. polyethylene, cross-linked polyethylene, polypropylene, ethylene-propylene copolymers), diene polyesters (e.g. polybutadiene, polyisoprene) or copolymers of dienes with copolymerizable monoethylenically unsaturated monomers e.g. gtyrene, acrylonitrile,

=:. '409811/1231 _BAD original

Isobutylene, vinyl pyridine, acrylic acid, acrylates, ethylene, Propylene, such as the butadiene-styrene copolymer, butadiene-acrylic tril copolymer, isobutylene-isoprene copolymer, Ethylene-propylene-diene / e.g. Dicyclopentadiene, ethylidene norbornene, Methylennorbornene, 1,4-hexadiene, cyclooctadieri / terpolymers). Such non-hydrocarbon polymers are also used stabilized, such as polyurethanes, polycarbonates, polyesters, polyvinyl chloride, styrene-acrylonitrile resin, ABS polymers. Of the compounds according to the invention, the esters and amines are preferred, while the amides are most preferred as they have the greatest impact as stabilizers for organic substances. En are 0.01 to 4 wt .-%, based on dps weight of the substrate of the invention Chemicals added to the substrates mentioned in order to protect them against the effects of air, heat and light. A synergistic protection is achieved by further addition of 0.01 to 4 wt .- / o, based on the substrate weight, one Dialkyl 3 »5'-thiodipropionate (the alkyl group being e.g. Has 0 to 20 carbon atoms), or by adding 0.1 to 5% by weight, based on the substrate weight, of a triaryl phosphite, in which each aryl group has one or two alkyl groups contains at least 8 carbon atoms. Such Ihonphites are described in U.S. Patent 2,733,226.

The ketones and alcohols according to the invention are suitable as intermediates for the preparation of other compounds of these Invention. The ketones of this invention include:

098 1 1/1231 eAO

1,5-di (3 '-ifiopj opyl-4 * -hydroxyphenyl) pcntanone-3 1, 5-di (3 ^l -fc-b <-ityl-4'-hydroxyphenyl) pentanone-3 1, 5-di ( 3 '-r.ec-butyl-4' -hydroxyphenyl) pentanone-3 1, 5-di / 3 '- (nlpha-methylstyryl) -4' -hydroxyphenyl / pentanone-3 1,5-di (3'-hexyl -4'-hydroxyphenyl) pentanone-3 1,5-di (3'-cyclohexyl - ^ '- hydroxyphenyl) pentnnon-3 1,5-di (3'-non;yl-4' -hydroxyphenyl) pentanone-3

1,5-di (3 '»5'-diisopropyl-4'-hydroxyphenyl) pentanone-3', 5 '-di-t-but, yl-4 * -hydroxyphenyl) pentanone-3, ^' - di- sec-butyl ^ '- hy ^ ¹ oxyphenyl) pentanone-3, ^' - di- (alpha-methylstyryl) -4 ^l -hydroxypheny] _i / pentanone-3

1, ^ - ^ 1 (3'-methyl-5'-butyl-4'-hydroxyphenyl) pentanone-3 1- (3 ', [3'-diisopropyl-4' -hydroxyphenyl) -5- (4 "-hydroxyphenyl ) -pentanone-3 1- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -5- (4 "-hydroxyphenyl) -pentanone-3 1- (3 ^I , 5 ^l -diiropropyl-4 '-hydroxyphonyl) - ^I 3- (3 ", 3" -di-t-butyl-4 ^fl hydroxyphenyl) pentanone-3 1, 5-üi (3'-i- ^r; opropyl-4- ¹ -hydroxyphenyl) - 2-ethyl-pentanone-3 1,5-di (3'-t-butyl-4'-hydroxyphenyl) -2-methyl-pentanone-3 1,5-di (3 '»5'-d it-butyl -4'-hydroxyphenyl) -2-methyl-pentanone-3 1,5-di (3'-mRthy1-5'-t-butyl-4'-hydroxyphenyl) -2-ethyl-pentanone-3 1,5- Di (3'-sec-butyl-4'-hydroxyphenyl) -2,4-dimethyl-pentanone-3 1,5-di (3'-eyelohexyl-4'-hydroxyphenyl) -2-methyl-4-ethylpentanone-3 1, S-Di (3 ', 5'-diisopropy1-4'-hydroxyphenyl) -2,4-dimethylpentanone-3-

40981 1/1231

The alcohols of this invention include:

1,5-di (3'-isopiopyl-4'-hydroxyphenyl) pentano 1-3 '1,5-di (3'-t-but.yl-4'-hydroxyphenyl) pentanol-3 1,5-Bi (3 '-soe-butyl-4' -hydroxyphenyl) pen tanol-3 1,5 ~ di / 3 '- (alpha-methylstyryl) -4'-hydroxyphenyl / pentanol-3 1,5-di (3'-hexyl —4 '-hydroxyphenyl) -pnηtano1-3 1,5-L) i (3' -cycloheyyl- ^/ 1- ^l -hydroxyphenyl) pentanol-3 1,5-üi (3 '- nonyl-4' -hydroxyphenyl) pentanol-3 1, ^r ) -Di (3 ', ^r j '-'J üropropy 1-4'-hydroxyphenyl) pentanol-3 1, 5-di (3 ', ^r j ' -d it-butyl- 4 '-hydroxyphenyl) pentanol-3 1,5-üi (3', 5'-di-rec-butyl-4'-hydroxyphenyl) ρentanο1-3 1, ^r ) -Di / 3 ', ^' -d i- (alpha-methylstyryl) -4'-hydroxyphenyl / -pentanol-3

1,5-di (3'-methy1-5'-t-butyl-4'-hydroxyphenyl) pentanol-3 ^ - (3 '» b '-diisQpropyl-4'-hydroxyphenyl) -5- (4" -hydroxyphenyl ) -pentano L-3

1- (3 ', ^t 3'-di-t-l'utyl-4' -hydroxyphenyl) -5- (Ί "-hydroxyphenyl) -pentanol-3

Ί- (3 ', y-d Ü! 3opropyl-4' -hydroxyphenyl) -5- (3 ",?" - di-t-butyl-4 "-hydroxy PiIeTIyI) PeHt anol-3

1, ^ - Di (3 '-i nopj-opy 1-4 ⁽ -liydroxyphenyl) -2-ethy 1-ptnt anol-3 1, ^r ,) - Di (3'-t-butyl-4' -hydroxyphenyl) -2-1 utyl-pentanol-3 1,5-di (3 ', 5'-di-t-butyl-4 ¹ -hydroxyphenyl) -2-methyl-pentanol-3 1,5-di (3' -methyl -!? '- t-butyl-4' -hydroxyphenyl) -2-propylpentanol-3

1,5-Di (3'-rrc-buty1-4'-hydroxyphenyl) -2,4- diethyl-pentanol-3

409811/1231

1,5-di (3'-cyclohexyl-4'-hydroxyphenyl) -2-ethy1-4-methy1-pentanol-3 1,5-di (3 ', 5'-rii-t-butyl-4-hydroxyphenyl) -2,4-dimothyl-pentanol-3 1,5-di (3'-pyroprnpyl - / ».'-hydroxyphenyl) -3- ^ ethyl-pentanol-, 3 1,5-di (3'-t-butyl -4'-hydroxyphenyl) -3-ethyl-pentanol-3 1, 5 - Di (3'-sec-butyl-4 -'-hydroxyphenyl) -3-propyl-pentanol-3 i ^ -Di / ^ '- Colpha-niethylstyryl) - ^ '-hydroxyphenyl / -3-butylpentanol-3 1,5-Ui (3'-hexyl-4'-hydroxyphenyl) -3-isopropyl-pentanol-3 1,5-di (3'-cyclohexyl -4 '-hydroxyphenyl) -3-cyclohexyl-p en tanol-3 1,5-di (3'-nonyl-4'-hydroxyphenyl) -3-phenyl-periLanol-3 1,5-di (3', 5'-diisopropyl-4'-hydroxyphenyl) -3-isopropy1-pentanol-3 1,5-üi (3 ', 5'-di-t-buty1-4'-hydroxyphenyl) -3-t-butyl-pentanol- 3 1,5-ui (3'-raethyl-5'-t-butyl-4'-hydroxyphenyl) -3-methylpentgnol-3 Λ , 5-ui (3'-XROρropy1-4'-hydroxyphenyl) -2.3 -dimethyl-pentanol-3 Λ , 5-di (3'-tb i1.yl-4 '-hydroxyphenyl) -2-rünthyl-3-ethyl-perjtanol-3 1,5-ui (3' -sec-butyl- 4'-hydroxyphynyl) -2 -; ^ ethyl-3-propylpentonol-3 1,5-di (3'-cycloh (? Xyl-4'-hydroxypheny l) -2-methyl-3-cyclohexylpentanol-3 1,5-di (3 ', 5' -cli-t-butyl-4 '-hydroxyphenyl) -2-methyl-3-t-butylpentanol-3 1, 5-di (3 ', 5'-dURopropyl-4'-hydroxyphenyl) -2-methyl-3-isopropylpentanol-3 1,5-di (3'-isopropyl-4 ¹ -hydroxyphenyl) -2,4-dimethyl- 3-ethyl-

^ 0981 1/1231 & Λ0 O? '^ ^{: 1? I}

pentariol-3 1, fj-Di (3 '-nee-Imty 1-4' -hydroxyphenyl) -2, 3,4-tri-methyl-pentanol-3 1, ^r ; -Üi (3'-t-buLyl- / i ¹ -hydroxyphenyl) -2,4-diethyl-3-butylpentanol-3 1,5-di (3 ', 5 ¹ -di-t-butyl-4 ¹ -hydroxyphenyl) -2,4-dimethylcyclohexyl-pentonol-3 1 , ^ - Di (3 ', D' - 'liir.opropy 1-4' -hydroxyphenyl) -2,3,4-trimethyl-pentanol-3 1,5-Üi (3'-methyl - ^ '- t- butyl-4'-hydroxyphenyl) -2,3,4-triethylpentanol-3

Esters covered by the invention include: 1,? - Di (3'-isopropyl-4'-hydroxyphenyl) -3-pentyl acetate üi / 1,5-di (3'-t-butyl-4'-hydroxyphenyl) - 3-penty] y succinate di / 1,5-di (3'-ff; c-butyl-4 ^l -hydroxyphenyl) -3-pentyl7-ß, ß ^l thiodipropion .- 't.

Di / i, 7> -di (3'-hoxyl-4'-hydroxyphenyl) -3-pent7 / l / phthalate Λ , ^ri -Di (3 ', | 3' - (Ii-t-butyl-4 '- hydroxyphenyl) -3-pentyl benzoate 1, 5-di (3 '»5' -d iir.opropy 1-4 '-hydroxypheny 1) -3-pentyl stearate 1,3-di (3'-methyl-5'-t- butyl-4'-hydroxyphenyl) -3-pentylbutyrate 1,5-di (3'-t-b'ityl-A'-hydroxyphenyl) -3-! -nethyl-3-pentyl acetate 1,5-di (3 ', 5 ^l -dURopropyl-4 ^l -hydroxyphenyl) -3-phenyl-3-pentylbenzoate 1,5-di (3'-iriopropyl ^ '-hydroxyphenyl) ^ -methyl ^ -pentyl acetate di / 1, S-di (3'-t -butyl-4'-hydroxyphenyl) -2-butyl-3-pentyl7-guccinate di / l, 5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -2-ethyl-3- pentyl / -phthnlate

«09811/1231

23Α4525

1,5-di (3'-methyl-1-5'-t-butyl-4-hydroxyphenyl) -2-methyl-3-pentyl stearate

1,5-di (3'-sec ~ butyl-4'-hydroxyphenyl) -2,4-diinethy 1-3-pentyl acetate

1 _t 5-di (3'-cyclohexyl-4'-hydroxypheriyl) -2,4-diethyl 3-pentyl benzoate

1,5-di (3'-isopropyl-4 '-hydrox ^' phenyl) -2,3-diulethyl-3-pentylbutyrate

1 ₁ 5-di (3'-t-butyl-4'-hydroxyphenyl) -2,3-dimethyl 3-pentyl benzoate

Di / i _t ⁽ ) -di (3 ^l , ^ '- di-t ^{-butyl-4 (} -hydroxyphenyl) -2,3-diinethyl-3-pentyl / succinate

1,5-di (3'ι 5'-diisopropyl - ^ '- hydroxyphenyl) -2,3-diraethyl-4-ethyl-3-peniylacetat

1,5-di (3'-methyl-5'-t-butyl-4'-hydroxyphenyl) -2,3,4-trimethyl-3-pentyl stearate

Aainc covered by the invention include:

Ν- / Ϊ, 5-di (3 '-iijopropyl-4' -hydroxyphenyl) -3-pontyl / -N-methyl-N-phenylamine

If / i, 5-di ( ^{3'-t-butyl-4 l} -hydrox3'phenyl) -3-pentyl7-N-ethyl-N-butylamine

Tri- / 1,5-di (3 '~ / alpha-methylstyryl / -4'-hydroxyphenyl) -3-pentyl / -ainine

Ν- / Ί, 5-di (3 '-sec-butyl- *!' -Hydroxyphenyl) -3-pentyl / -N-n-octadecylamine

BAD OR! G! MAL

4 0 9 811/12 31

N- / 1,5-di (3'-h ^ xyl-4 ^l -hydroxyphenyl) -3-pentyiy-Nn-hexylamine Ν- / Ϊ, "v-di (3 '-cyclohexyl- ^' -hydroxyphenyl) - 3-penty 1 / -N-CyClO-hexylainine

Njll'-di / i, S-di (3'-nonyl-A -'-hydroxyphenyl) -3-pentyl, 7hexamethylene diamine

N, N'-di / i, 5-fl i (3 ', ^r ?' - diisopropyl-V-hydroxyphenyl) -3-pentyl / -at.hylenediam.iti

N ₁ N ¹ -di / i, ';- (! I (3', 5 '-d it-butyl-'i' -hydroxyphenyl) -3-pentyl7-propylenediamine

Ν- / Ϊ, 5-cU (3 ', ^' - di-Bec-butyl - ^ '- hydroxyphenyl) -3-pentyl7-N-butylamine

N-Zi ₁ 5-tli (5 ^l -inoLhyl-5 ^l -t-butyl-'i '-hydroxyphenyl) -3-pentyl7-N-ynethylamine

N-Zi-C3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -3 - (^ "- hydroxyphenyl) 7-3-pentylamine

1, S-di (3 '-ir.opr-opyl- ^' -hydroxyphenyl) -2-met.hyl-3-pentylarain N-Zi, 3-di (3 '-L-butyl-4' -hydroxyphenyl) -2-; ethyl-3-peniyl7-H-mefchylamine

NZ "i, S'-di (3 ', 3'-cli-t-butyl-4 ^l -hydroxj'phenyl) -2-raethyl-3-pentyl7-N, Nd i ät hy 1 aia i η

1,5-Di (3 '-iPopropyl-4' -hydroxyphenyl) -2, ^ t -dimethyl-3-pentylainine

pentyl_7-N-methylamine

Typical amides falling under the invention include: N-Zi, 5-di (3'-i ^ opT'opyl - '+' - hydroxyphenyl) -3-pentyl7-N-n-octadccylrtearamide

SAD

60981 1/1231

If 234A525

Ν- / Ϊ, 5-di (3 '-f; -butyl-4' -hydroxyphenyl) -J-pcntylZ-N-n-octylbutyramide

1Τ- / Ϊ, r'-di (3 ^l -i - '"c-butyl-4' -hydroxyphonyl) -3-pentyl / -N-noctadecyl acetate fuiid

N, N'-di / ^ 1,5-di (3'-hexyl-4'-hydroxyphenyl) -3-pentyl / -N ₁ N'-diactylethylenediarain

Ν- / Ϊ, ^r ; -di (3'-cyclohexyl- ^ · '-hydroxyphenyl) -3-pentyl / -licyclohexylpropLonauid

Ν, Ιί '^ ί / Ί, ^ - Λι (3 ^l -üonyl-4 ^l -hydroxyphπnyl) -5-pontyl / -lί, N ^I -

Ν- / Ί, 5-di (3 ', 5' -di-isopropyl-4 ^l -hydrnxypher; yl) -3-pentyl / -N-bu ty 1 ε te ar am id

N- / 1, ^r i-r3i (3 ^l , ^rI -di-t-butyl- ^ '-hydroxyphenyl) -3-pentyl / -butyramide

Ν- / Ί, 5-di (3 ', ^: .' -Di-sec-butyl- ^ '-hydroxyphenyl) -3-penty 1 / -N-methy1acetamide

Ν- / Ί, 5-di (3 ^l -iethyl-5'-t-butyl-4'-hydroxyphenyl) -3-pentyl7-N-butylbenzamide

!!, N'-di / i ^ -diC ^ ^{1, c;} '-di-t-butyl- ^' -hy lrox ^ -phenyl) -3-pentyl7-succinamide

N, N ^l -di / 1,5-di (3 ', 5'-diisopropyl-4'-hydroxyphenyl) -3-pentyl7 ~ ß, ß'-thiodipropionamide

Ν- / Ϊ, 5-di (3 ^l ₎ 5. ^l -di-t-butyl-4 -'-hydroxyphenyl) -2-methyl-3-pentyl7-benzenesulfonamide

N- / i, ^ - di (3'-isopropyl-4 ¹ -hydroxyphenyl) -2-methyl-3-pentyl-7-N-methylacetamide

409811/1231

N- / i, ^r 5-di (3'-t-butyl-4-hydroxyphenyl) -2-methyl-3-pentyl / -Nn-butylbutyramide

Ν- / Ί, 5-di (3'-isopropyl-4'-hydroxyphenyl) -2,4-dimethyl-3-pentyl-7-stearamide

N / i, 5-di (3 ^I ₁ 5 ^I -di-t-butyl-4 ^t -hydroxj'phenyl) -2,4-dimethyl-3-pentyl / -N-methylacetamide

Useful for creating the connections according to the invention 1 entadieiione include:

1,5-di (3'-isopyl-4'-hydroxyphenyl) pent ad ieri-1,4-one-3 1,5-di (3 ^l -t-butyl-4'-hydroxyphenyl) pntndiene-1 , 4-on-3 1, ^t ,) - Üi (3 ^l -cycloijoxyl-4 '-hydroxypheiiyl) pentadien-1,4-one-3 1, l-Di (3', Γ '' -diisopropyl-4 ' -hydroxyphenyl) pentadien-1,4-one-3 1,5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) pentadien-1,4-one-3 1, ^r ) -i 'i (3'-ffietliyl-5'-t-butyl- ^' -hydroxyphenyl) pentadien-1,4-one-3 1,5-di (3'-isopropyl - ^ '- hydroxyphenyl) -2-methylpentadiene- 1 _t 4-one-3 1,5 - di (3 ', 5'-d it-butyl-4' ~ hydιόxypliοnyl) -2-methylpentadien-1,4-one-3
1,5-di (3'-methyl-5'-t-butyl-4'-hydroxyphenyl) -2-methylpentadiene-

1,5-di (3'-t-butyl-4 '-hydroxyphenyl) -2,4-clime thylpentadiene-1,4-

1,5-di (3'-hexyl-4'-hydroxyphenyl) -2,4-di, T. ethylpentadien-1,4-one-3

1,5-di (3 ' ₅ 5' - <"* iisopropyl-4 '-hydroxyphenyl) -2,4-dimethylpentadiene-1,4-OI1-3-

^ 0981 1/1231

- • -

The following are generalized manufacturing methods given for certain compounds according to the invention: N - / ^, 5-di (5 *, ^ '- di-hydrocorbyl- (4' -hydroxyphenyl) -3-pentyl / -N-hydrocarbylamine

1.0 mol of 1,5-di (3'ι 5'-di-hydrocarbyl-4'-hydroxyphenyl) pentanone-3 , 10 g Fd / C filled. The mixture was heated from room temperature to 125 ^° C. under 28 to 56 atm of hydrogen for 1 to 5 hours.

The catalyst was filtered off and the alcohol was removed under reduced pressure. The residue was dissolved in hot stone and left to cool. The received Aline was separated by filtration.

Ν- / Ί, 5-di (3 ', 5' -di-hydrocarbyl-Ί- '-hydroxyphenyl) -3-pentylZ-N-hydrocarbyl-N-hydrocarbylamine

In a rait thermometer, mechanical stirrer, dropping funnel and condenser equipped four-neck flask with a capacity of 2 liters, 1.0 Hol Ν- / Ϊ, 5-di (3 ', 5'-di-hydrocarbyl-4'-hydroxyphenyl) -3-pentyl7-N-hydrocarbylamine, 1.0 mole of triethylamine and 1000 ml of a hydrocarbon solvent were charged. To this stirred solution was slowly added 1.0 mole of a hydrocarbyl halide, with cooling if necessary. After all of the halide had been added, the Mixture refluxed for 2 to 4 hours. The triethyl

A 0 9 8 1 1/1231

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amine hydrochloride was separated by filtration and the Solvent removed under reduced pressure; The return " was dissolved in hot hexane and allowed to cool. The tertiary amine was separated off by filtration.

Η- / Ί, 5-di (3 ', 5' -di -hydrocar by 1-4'-hydroxyphenyl) ~ J> - pentyl / -N, N-di-hydrocarbylamine

1.0 mol of 1,5-di (3 ',?' - di-hydrocarbyl-4'-hydroxyphenyl) -3-pentylainine, 2.0 moles of triethylamine and 1000 ml of a hydrocarbon solvent are filled in. To this stirred solution was slowly added 2.0 moles of a hydrocarbyl halide, with cooling if necessary. After all of the halide had been added, the mixture was refluxed for 2 to Ί hours. The triethylamine hydrochloride was removed by filtration υΐνΐ the solvent under reduced pressure. The residue was dissolved in hot hexane and left to cool. The resulting tertiary amine was separated by filtration.

1,5-di (3 ', ^' - di-hydrocarbyl-4'-hydroxyphenyl) -3-hydrocarbyl-3-pentyl ester

1.0 mol of 1,5-Üi (3 ', 5 ^r -di-hydrocarbyl-4'-hydroxy-

(09811/1231

phenyl) -3-hydrncarbylpentanol-3, 1.0 mole of triethylamine and 1ÜÜÜ ml of a K ^ hlenwasserstoff-Solvent filled. To this stirred solution was added 1.0 mole of a coic acid chloride. After all of the GäurecMorid had been added, the mixture was refluxed for 2 to 4 hours and the diethyl run in hydrochloride was removed by filtration, the solvent was removed under reduced pressure and the residue was dissolved in hot hexane and allowed to cool. The ester was left to cool separated by filtration.

Ν- / Ί, 5-di (5'ι 5'-dihydrocarbyl-4'-hydroxyphenyl) -J-pental / -II-bydrocorbylamide

In a .axt thermometer, mechanical stirrer, dropping funnel and condenser, four-necked flask with a capacity of 2 liters was added 1.0 mol N- / ~ 1,. ^r * -di (; 5 ', 5' -d i-hydrocarbyl-4'-hydroxyphenyl) -3-pentyl7-N-hydroC'Trbyla'nin, 1.0 hol triethylamine and 1000 ml carbon hydrogen solvent. To this r; e, stirred solution, 1 C Hol gure chloride was added. After all of the acid chloride had been added, the mixture was refluxed for 2 to 4 hours. The triethylamine hydrochloride was removed by filtration; the solvent was removed under reduced pressure. The residue was dissolved in hot hexane and allowed to cool. The amide was separated by filtration.

General methods for the preparation of the intermediates which can be used according to the invention are given below:

40981 1/1231

^eAD ORIGINAL

-y -

1,5-di (3 ', b '-di-hydrocarbyl-4'-hydroxyphenyl) pentadien-1,4-one-3

In one with a thermometer, mechanical stirrer and cooking inlet tube With a condenser equipped three-neck flask of 2 liters capacity, 1.0 mol of 3, iJ-Di-hydrocarbyl ^ -hydroxybenzalclehyd, 0.5 Hol of a ketone and 1000 ml of solvent filled. For 3 and 4 hours, hydrogen chloride was used as in blow in the mixture while the temperature rises to 0 to 15 ° G was held. The reaction noise was then in ice water and the pentadienone was separated off by filtration. The lentadienone was then crystallized from alcohol.

1, ^ - Di (3 ', 5'-di-hydrocarbyl-4 ^l -hydroxyphenyl) pentanone-3

1.0 mol of 1, 5-di (3 ', 5'- ⁽ⁱ J-hydrocarbyl-4'-hydroxy phcnyl) pentadiene-1,4-one-3' 1000 ml alcohol and 28 g of nickel on Kier, elf_, filled clock. The mixture was heated for 1 to 5 hours under 28 to 5G at hydrogen to 50 to 125 ⁿ g. The Peritanon-3 was umkristallifiieit from alcohol.

1,5-di (3 '1- ¹ ' -di-hydrocarbyl-4 '-hydroxyphenyl) pentanol-3

In a cooling autoclave of 3 »73 1 content were 1.0 mol 1,5-di (3 ', 5'-di-hydrocarbyl-4-' -hydroxyphenyl) pentadien-1,4-one-3, 10 κ of a f '/ o-i ^ cn Tallaciiums on Kohlo and. "1000 ml of one Filled with alcohol. The mishun, ", was taking 1 to 5 hours 28 to 56 at hydrogen heated to 125 ° G.

811/12 31 ^AL

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The catalyst was removed by filtration; the Alcohol was removed under reduced pressure. The residue was dissolved in hot hexane and then the hexane solution to cool down. The pentanol-5 was obtained by filtration severed.

1,5-Di ( ⁷ J ', 5' -di-hydrocarbyl- ^ '-hydroxyphenyl) -3-hyd "ro-. C nr byl -p ^fi nt nnol-3

In a with a thermometer, mechanical stirrer, dropping funnel four-necked flask equipped with a condenser of 3 1 content were 1.1 moles of magnesium turning chips and Filled 1ÜCO ml of diethyl ether. This was slow 1.0 ha of an alkyl or aryl halide added. After this all of the ilalodenide was added, became the Grignard reagent a gunde boiled under reflux.

The Minohnnc was then cooled to Ciniraertemperature, and 1, ü Ποί 1,5-Μ (3 ', <) ' - (Uhydrocarbyl-4 '-hydroxyphenyl) pentanone-3 in 10 ml of diethyl ether were slowly added to the Grignard ßeaßens, so that there was a constant reflux. After all of the Pent; anon-3 had been added, the reaction vessel was refluxed for 2 hours. The mixture was cooled and then poured into egg water. This Iliecliunr; was then acidified and the layers separated. The diethyl ether layer was dried and then the ether was removed under reduced pressure. The residue was dissolved in hot hexane and allowed to cool

4 0 9 8 11/12 3 1 bathroom original

permit. The tertiary alcohol was separated off by filtration.

The invention is further illustrated by the following examples explained:

Example 1 3> ^ -Üi-t-buty I - '! - hydr oxy benzaldehyde

GOü c 2,6-di-t-butyl-p-cresol and JGCO ml t-butyl alcohol were poured into a four-necked flask with a capacity of 5 liters, equipped with a thermometer, mechanical stirrer, dropping funnel and venting tube. This stirred solution was added to 900% _{Br 0} at 25 to 35 ° C. over a period of 10 hours. The resulting solid was separated by filtration, washed with hexane and dried. The yield was -40 g (71 %) of aldehyde with a melting point of 1G7 to 1C) ⁰ C.

example P.

1,5-di (3 ', 5'-di-t-butyi-4'-hydroxyphenyl) pentanone-3

200 g (0.400 mol) 1, T-Di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -pentadiene-1,4-οη- 3, 1200 ml of isopropanol and 20 ^ of a nickel catalyst (^ O % Ni / Kieselcuhr) filled. The mixture was 1,2Γ> hours under hydrogen at 40 to 50 to 100 ⁰ C.

«0981 1/1231

-S-

heated; 0.79 Hol (97 %) hydrogen was absorbed.

The oil was heated to boiling and filtered to separate off the catalyst. After cooling, the hydrogenated ketone was separated off. The yield was 192 g (97 %) \ the product melted at 138 to W ^{0 0} O.

Example 5

', 5'-di-t-butyl-4'-hydroxyphenyl) pentanol-3

200 pounds of 1,5-di (3 ', 5'-di-t-butyl-' + '-hydroxyphotiyl) pentadiene-1,4-ΟΠ-3, 1200 ml of isopropanol were placed in a 3 // Ώ 1 volume autoclave and fills £ 10 5% Id / G. The reaction proceeded for 2.75 hours at room temperature below 29.5 to 0.5 hours of hydrogen; 1.11 Hol (91 %) of hydrogen was absorbed.

The catalyst was separated off by filtration and the isopropanol was removed under reduced pressure. The residue was dissolved in hot hexane; The air was left to cool down. Dr-r cebildete alcohol was separated by filtration and removed. The yield Iac at 180 g (89%) j the melting point was 129-130 ⁰ C.

example ¹ V

1,5-di (V, 5'-di-t-butyl-V-hydroxyphenyl) -3-pintyl acetate

In one with thermometer, mechanical stirrer and condens Three-necked flasks with a capacity of 500 ml were cooler

811/12 31 ^BAD original

23AA525

50 g (ϋ, 061 mol) 1,5-Μ (3 ', γ-di-t-butyl ^' - hydroxyphenyO-pentanol ^ um] 2 ^ 0 ml of enetic anhydride were poured in. The mixture was 4 hours on a steam bar! heated to 90 ⁰ C. After cooling, the mixture was poured into water. It was separated a substance which solidified on standing. the melting point was 82 to 85 ° C.

example 5

1,5-di (3 '»5' -fii-t-butyl-4- ^l -hydroxyphenyl) -3-pentyl acetate

In a three-necked flask with a capacity of 500 ml, which had been eradicated with a thermometer, mechanical stirrer and condenser, were 18. (0.03 ^ 1 hol) 1,5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -pentanol-3 » b-, 5 β (0.07 mol) acetyl chloride and 2 ^ 0 ml of benzene was poured in. The mixture was refluxed on a steam bath for 6 hours.

The solvent was removed under reduced pressure and the oily residue is chromatographed on aluminum oxide. That isolated product was an oil. The IH spectrum was in agreement with the product of Example 1, which is obtained from acetic anhydride had been made.

Example 6

1, T> -Di (3 ', 5'-di-t-buty 1-4'-hydroxyphenyl) -3-pentylste.arate

In one with a thermometer, eiiiGffi mechanical stirrer and condenser „ _ΛΓ , _Ύ ν ^ αϊπ

409811/1231

23U525

equipped three-necked flask of 500 ml content were 10.0 g (0.02 Hol) 1, S-Di (3 ', 5' -di-t-butyl-'i'-hydroxyphenyl) * - Pentanol-3, 10.0 g stearoyl chloride and 250 ml xylene. The mixture was refluxed for 8 hours, then cooled, with aqueous (6N) sodium hydroxide and finally with Water washed. The xylene was removed under reduced pressure and the residue uiiikristallisiert from hexane. The stearate is a waxy solid; Melting point 52 to 54- G.

Example 7

1, S-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -3-pentylbenzoate

10.0 g (0.02 mol) of 1,5-di (3 ', 5' - <5i-t-butyl- 4 ^l -hydroxyphenyl) -pentanol-3, ^r >, C g benzoyl chloride and 250 ml xylene filled. The mixture was refluxed for 8 hours and then cooled. The brine was washed with aqueous (G n) sodium hydroxide and then with water and dried over sodium sulfate. The xylene was removed under reduced pressure and the residue was recrystallized from hexane. The product yield was 7.5 g; Melting point 115 to 11G ⁰ G.

Example 8

Di / i, S-cli (3 ', "Γ ·' -di-t-butyl-Λ * -hydroxyphenyl) -3-pentyl / succinate

In a thermometer, mechanical stirrer and condenser

4 09811/1231 ^ - '^

234A525

aur.f cooler; he: (? 0.0 IW) tM, dead three neck KOLBON of 500 ml content, 10.0 g of 1,5-DiO ^1, 5'-di-t-butyl-4'-hydroxyphenyl jpentrnol -3, Ί »IT 'C (0.01 Hol) succinic acid chloride and 250 ml of xylene filled. The mixture was refluxed for 8 hours. After cooling, the mixture was washed with sodium hydroxide and water. The xylene layer was dried over sodium sulfate and then xylene was stripped off under reduced pressure. The residue was recrystallized from hexane. 7.9 C succinate was isolated; [Melting point 1/2 to 13> 3 ° C

JÜi (1,!: - li (5 ',' '' - tU-i-tuty 1-4 '-hydroxyphenyl) ~ 3-pentyl adipate

1 ^, 0 G (O _- , 03 Hol) 1, 5-Di (3 ',?' -Di-t-buty 1- 4 '-hydroxyphenyl) -pentnnol- ?, ² S ₁ O r, (0.01G mol) adipyl chloride and 2f> 0 ml toluene filled. The mixture was refluxed for 5 hours at untex *. After cooling down, the flischunr; washed with sodium hydroxide and water and then dried over sodium sulfate. Unr toluene was stripped off by distillation and the oily Rückptond on aluminum oxide was chromatographed. The refractive index was Njj »1.502. There? IR spectrum and nuclear magnetic resonance spectrum indicated that the isolated oil was the desired product. The IR Gpc'rtrum had the following characteristics:

BATH ORIGINAL

409811/1231

H 23U525

2.7 μ hindered phenol band

3.35 µ CH band

5.7 µ ester carbonyl band

6.9 / ι phenyl nucleus band

12.6-1? / U phenyl substitution band

The curve of the learning metrics resonance gave the following Information:

6.9 Δ 4'henyl protons

5.0 Δ 1 methine proton

4.9 Δ 2 phenolic protons

2.7-1.6 A 12 methylene protons

1,4 & 36 t-butyl protonon

These parameters correspond to the expected values.

1Ü

- ^ '-hydroxyphei} yl) -3-peutyl / -

phthalate

In one with thermometer, stirrer and inechanir.chem Kondenskühler auRcertfitteten three neck flask of ^r) 00 ml were 24.8 G (0.0? Hol) 1,5-di (3 ',! 3 ^l di-t- butyl- ^ '-hydroxyphenyl) pentanol-3, 5.3 U thaloyl chloride and 250 ml of toluene filled. The help was refluxed for 8 hours and then allowed to cool.

The ilinchunc was washed with sodium hydroxide and water and then dried over sodium sulfate. Dan was taking toluene

4 0 9 811/12 31 bad original

Draw off under reduced pressure. The product was chromatorraphiert on aluminum oxide; an oil was isolated. The ester solidified on standing; Melting point 82 to 05 ° C. The III spectrum un <! the nuclear magnetic resonance spectrum showed that diene was the desired product. The IR curve had the following characteristics:

2.7 μ hindered phenol band 5.75 ρ ester carbonyl band 6.95 ρ phenyl core band

12.6-13.0 / n phenyl substitution band

The nuclear magnetic resonance curve provided the following Information:

7.4 Ά 4 o-substituted phenyl protons

6.85 Λ 8 m-phenyl protons

5.1 Zl 2 methine frotons

4.8 Δ. 2 phenolic frotons 2.7-1.0 Δ 16 hothylene irotoneu 1.4 Λ 72 t-butyl protons

These parameters correspond to the expected values.

Example 11

Di / 1,5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl ) -3-pentyl7-ß, ß ' -thiodipropionnt

In one with one ». Thermometer, mechnni r.chem stirrer and ion-cooling cooler aur ^ erntt ^ tm three-hole flask of 500 zl content

SAD ORIGINAL 4 0 9 8 11/1231

23U525

were 15 ζ (<- \ üJ> mol) 1,5-di (3 *, 5'-di-t-butyl-4'-hydroxyphenyl) pentanol-3, 3 »3 G ß, ß'-thiodipropionyl chloride and ? ^> 0 ml of xylene filled. The mixture was refluxed for 8 hours and allowed to cool over a period of time. The solvent has been removed. The product was chromatographed on aluminum oxide and an oil was irolized. Refractive index N ^ ^y a 1, ^ 12. The IK spectrum and the inacnetic nuclear regime indicated that this was the desired product. The IR curve had the following characteristics:

2.7 ü hindered phenol band

5.7 | J ester carbonyl band

C, 9 .μ phenyl-crenate ends

Ί2, Γ) -15, Ο μ phenyl substitution band

The nuclear magnetic resonance curve provided the following information:

6.9 ^r ; / ^ 4 phenyl protons

5.1 ^ 1 Hethin-Iroton

f ', 0 ^ 1 phenolene proton

2.7-1 /> / ü. 12 methylene protons

1.4 A 56 t-butyl protons

These parameters correspond to the expected values.

_ßAD

40981 1/1231

"* '" 234A525

Example 12

Tri / Ϊ, 5-di (3 ', ^r >' -di-t-butyl-4 '-hydroxyphenyl) -3-pentyl / -phosphite

In a lait thermometer, mechanicala stirrer and condenser equipped three-neck flasks with a capacity of 500 ml 15 ε (0.03 M »D 1,5-di (3 ', 5'-di-t-butyl-4' -hydroxyphenyl) -pentanoV3, Filled with 25 ml of triethylamine and 250 ml of chloroform. To this stirred mixture became 1.4 g of phosphorus trichloride adds. The reaction was exothermic. after the When the exotherm had subsided, the mixture became

Boiled under reflux for hours and then cooled.

The mixture was washed with water, dried over sodium sulfate and the solvent under reduced pressure Pressure removed. The residue was recrystallized from ethanol-water and resulted in a fertec product with a melting point of 117 to 12 ° C. Ihopphornalysis: calculated 2.05; found 2.1. The IR spectrum and the magnetic one The nuclear renonane spectrum confirms this structure. the The IR curve has the following characteristics:

2.75 γ hindered phenol band

3.35 C-H sands

6, ⁽ J5 μ phenyl nucleus dande

9.0 and 10.5 µ P-u-0 band 12.6-13 »O ρ phenyl substitution band

4098 Ί1 / 1231

The nuclear magnetic resonance curve provided the following information:

6.95 ^ 4 aromatic protons

4.95 Δ 2 phenolic protons

4.3 / \ 1 methine proton

2.7-1, ^r ^ V 8 methylene protons

1, '+ ZX JG t-Butyl-I ^j rotoner:

These parameters correspond to the expected values.

Example 13

1,5-üi (3 ', 5'-di-t-butyl-4'-hydroxyphpnyl) -3-pentylamine

113 S (0.229 NoI) 1,5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) pentanone, 3 ^ ml ammonium hydroxide (50%) , 1200 ml of isopropanol and 13 0 Γν ^ -ϊ '^ σ palladium on carbon (Pd / G) filled. The mixture was for 2 hours under 53 ^C) t ^ hydrogen at 125 ° C erhitzl. 0.247 moles of hydrogen were absorbed.

The mixture was filtered to remove the catalyst and the isopropanol was removed under reduced pressure ab ^ ezofj ^ n. The residue was dissolved in hot hexane and the Let it cool down. The amine was separated off by filtration. The yield was 74 c, melting point 110 C.

BAD ORfGiNAl 40981 1/1231

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Example 14

-/ Ϊ, r ^ -Di (3 ', ^r -'-'Ut-butyl-4'-hydroxyphenyl) -3-pentylJ | -N- "raethylamine

In a stirred autoclave with a volume of 3.70 liters, 200 g (0.405 mol) of 1,5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -pentanone-3, 7t' ml of 40% - ices methylamine, 1000 ml of isopropanol and 13 £ 5 7 "ld / C was charged. The mixture was heated 5.5 hours under bir 41.5 45.3 Qt hydrogen at 55 to 60 ⁰ g., 0.3? mol of hydrogen absorbed.

The catalyst was separated off by filtration and the iFopropniol removed under reduced pressure. The residue was dissolved in hot hexane and allowed to cool. Since there was no separation of solids, the hexane solution was saturated with hydrogen chloride. This gave 1BG (3 Ariinhydrochlorid, Gchmclzpunkt 202 to 204 ⁰ C.

By treating the amine hydrochloride with a Bace the amiri was recovered. The viscous residue was in hot hexane and leave to cool. The solid amine melted at 127-129 ° C.

Example 15

N - / 'i, 5-di (3 ^l , 5 ^l -di-t-butyl-4- ^l -hydroxyphpr.yl) -3-pentyl7-Nn • butylamine

Tn a stirred autoclave with 3.7 "1 content

BAD ORIGINAL 4 0 9 8 1 1/1231

200 e (0.40? Mol) 1,5-di (3 ', 5 ^l -di-t-butyl-4'-hydroxyphenyl) -pentanone-5, 3 ^Γ · [j n-butylamine, 1200 ml isopropanol and 15 G 5% l'd / ΰ filled. The mixture became 0.75. Hours under 43.5 nt hydrogen to 90 ⁿ C and then 1.25 hours under 47 atm hydrogen to 125 ° C. Eg 0.4 mol of hydrogen was absorbed.

The catalyst was separated off by filtration and the isopropanol was removed under reduced pressure. The residue was dissolved in hot hexane and cooled. Since no solid separated out, the hexane solution was saturated with gaseous hydrogen chloride. This gave 164 g of amine hydrochloride with a melting point of 177 to 180 ^° C.

Treatment of the amine hydrochloride with a base and extraction with hexane regenerated the amine. The hexane was evaporated under reduced pressure and the residue allowed to stand, whereby it solidified. The solid melted at 79.bis 82 ⁰ C.

Example 16

Ν- / Ϊ, 5-di. (3 \ 5 '-di-t-butyl-4' -hydroxyphenyl) -3-pentyl / -N-noctylamine

154 g (0.312 mol) of 1,5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) pentarr were placed in a shaking autoclave with a capacity of 1.7 l 45 g octylamine, 330 ml isopropanol and G g 5% Pd / G filled.

0 3 811/12 31 bad original

33 23U525

The mixture was heated to 115 to 120 ° 0 for 5 »25 hours under 47.5 to 52.2 atm of hydrogen. -QS% of the theoretical amount of hydrogen was absorbed.

The catalyst was separated off by filtration and the isopropanol was removed under reduced pressure. The residue was dissolved in hexane and treated with gaseous hydrogen chloride. The yield of amine hydrochloride was 157 c; the melting point log at 113 to 120 ⁰ G.

By treating the amine hydrochloride with a base

and extraction with hexane, the amine was regenerated. Of the

pq
Refractive index was Njj = 1,507.

Example 1?

Ν- / Ί, 5-di (3 ', 5 * -di-t-butyl-4 ¹ -hydroxyphenyl) -3-pentyl / -N-noctndecylaniine

200 g (0.405 Hol) of 1,5-di (3 ', 5'-di-t-butyl-4-hydroxyphenyl) -pentonone-3, 112 g of n-octadecylaiiiin, Filled with 245 ml of isoproponol and 10 g of 5 % I'd / C. The mixture was heated to 115 to 120 ° G under 49 to 56.2 nt hydrogen for 5 hours. There were approximately abrorbiert 0.34 moles of hydrogen.

Since a solid separated, the mixture was heated to boiling to redissolve the solid and the catalyst was separated by filtration. the

4 0 9 811/12 31 BAD ORIGINAL

Mixture was left to cool and the product through Filtration -ib ^ efcrennt.

The product was dissolved in acetone to remove the insoluble unreacted octadecylarain. Dos acetone was then removed under impeded pressure, and the residue was inlöst in hexane (and treated with hydrogen chloride The resulting amine hydrochloride narrow:. ', At 102 to 104 ⁰ C.

The amine was regenerated by r.eharidlunrj the amine hydrochloride with a base. The Amiη melted lei 60 ⁰ C.

Example 18

cyclohexylamine

In a stirring autoclave of 3? The contents were 200 g (0.405 mol) 1, r, -Di (3 ', y-di-t-butyl-V-hydroxyphenyl) -pentanone-3i ' - ^ 7 6 cyclohexylnmin, 1200 ml 2-propanol and 15 ε 5 7o I'il / G filled in. The Ilischunr; was heated to 125 ° C for 3.75 hours under 48.6 bir- 51 atmospheres of hydrogen. 0.47 Hols of hydrogen were absorbed.

The catalyst was separated by filtration and the isopropanol was removed under reduced pressure. Of the The residue was dissolved in hexane and treated with hydrogen chloride. The resulting amine hydrochloride melted at 210

409811/1231 BAD

bio 213 ⁰ C

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The amin was regenerated by treating the Ar.iinhydrochloride with a barn. The ainin melted at 118 to 120 ⁰ C.

Elemental analysis:

Calculated: G 81.05 H 10.99 N 2.42

Found: G 80.96 II 11.04 N '2.48

Example 19

N, N '-üi / ΐ, 5- · 3i (3' »5 '-di-t-butyl-4' -hydroxyphenyl) -3-penty \ J- ethylenediamine

In a Kiihrautoklaven 3i? 8 1 contents were 200 G (0.405 Hol) 1,5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -pentanon-3, _t i? 2 B Ethyl end i ami η, 1075 nl inopropanol and 25 β 5% -issee I latin on carbon (i ^J t / G) filled. The mixture was under 2 ^hours; κΊ bip Ό, 5 at hydrogen ^{heated to r} O'G. 0.30 moles of hydrogen were absorbed in iCn.

The catalyst was separated off by filtration and the inopropanol was removed under reduced pressure. The residue was celöst in hot hexane to give upon cooling Frodukt 125 C with a melting point of 68 to 70 ° C.

A09811 / 1231

^ ₆ 23U525

Example 20

Ν, Ν'-ΰΐ / ί, ^ - ί'J (V, 5'-ai-t-butyl-4 '-hydroxyphenyl) -3-pentyl / propylenedininine

100 g (0.203 Που 1,5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -pentanone-3i 7 »4 g propylenediamine, 475 ml isopropanol and 10 3 5% ld / filled v. The mixture was 6.5 3t and 46 to 54 en under hydrogen at 115 am -on heated 120 ⁰ G.

The catalyst was separated off by filtration and the Iropropanol removed under reduced pressure. Of the Hückstari'l was dissolved in hexane and treated with hydrogen chloride treated. The resulting amine hydrochloride melted on

The Ar ;, in was regenerated by treating the amine hydrochloride with a base. Dan Am in melted at C2 to CA ⁰ Q,

Example? 1

N, N'-Di / i, 5-di (3 ', 5'-di-t-butyl- ^ l'-hydroxyphenyl) -. ^ - pentyl / -hexamet ^ ylenediarain

In a gas autoclave with 1.7 l capacity 34, f. J; (0.17 Hol) 1, 5-di (3 ', 5' -di-t-butyl-'i '-hydroxyphenyl) -pentanone-3, }, 'j> "Ilexamethylendiaiiin, 500 ml isopropanol and 10 g of 5% Id / G filled in. The mixture was taking 5 hours 48.5 to 53 atm of hydrogen heated to 100 to 105 ° G. It was

BATH 40981 1/1231

absorbs the 0.22 Hol of hydrogen.

The catalyst was removed by filtration and the isopropanol was drawn off under reduced pressure. The residue was dissolved in hexane and treated with hydrogen chloride. The resulting Amlnhydrochlorid melted at 228 to 23O ⁰ G. The Am.in was Major-ch-treatment freír eßetr.t of the amine hydrochloride with einef base. An oil was isolated.

Example 22

1 ^ 1, 5-di (3 \ 3'-cli-t-butyl-V-hydroxyphenyl) -3-pentyl / -ncetanide

In one with a thermometer, mechanical stirrer and condenser three-necked flasks with a capacity of 500 ml 30 g (0.061 hol) 1,5-di (3 \ 5'-di-t-butyl-V-hydroxyphenyl) -3-pentylamine, 250 ml acetic acid and 20 ml acetic anhydride filled. The mixture was refluxed for 5 hours and allowed to cool. The mixture was in Poured water and removed the product by filtration. The solid was recrystallized from isopropanol-water. The amide yield was 25 g and the melting point was around to °

Elemental analysis:

calculated: G 70.16 Ή 10.31 N 2.60 found: C? 6.1 '/ H 10.30 N 2.35

40981 1/1231

Example 2?

N- / 1,5-di (3 V ^l -fU-t-butyl-4'-hydroxypheriyl) -3-pentyl7-stearamide

In a. Perforated flasks of 500 ml capacity were filled with 40 {$ (0.031 Hol) 1,5-di (3'i5 ^l -di-t-butyl-4 ^l -hyflroxyphenyl) -3-pentylmuin, ΓΟ ml triethylamine and JGÜ; al hexane. Decoder Winchuii ;, were Kühren 30 (j- ^ Stenroylchlorid zuf enetat. After π tv / a half an hour WUR · ^"1 ^ the ^ Ilifichun nehr thick. Hie thread 1 1 diluted and brought to the boil. ^ ³ Triäthylr- The hydrochloride was removed by filtration and the solution was allowed to cool. The amide separated off and was removed by filtration and dried; melting point 105 to 107 ° C.

El em en t r ι an al yse:

calculated: G 80.56 II 11.50 N 1.84

found: C 80.15 ΙΓ 11.57 U 2.00

Example 24

Ν- / Ί, 5-υχ (3 ', ^Γ ' -di-t-lutyl-Λ ^l -] iy (3roxyphenyl) -3-pentyl7-N- / aethyl acetamide

In one with thermometer, mechanical mixer and condensation cooler equipped three-necked ilobes with a capacity of 500 ral 50 G (0.0'33 Hol) lI- / i, 5-di (3 ', 5'-di-t-b-jtyl- / ·)' -hydroxyphenyl) -

in, 150 ml er.ic acid > n \ d 15 ml er.sigsäure-

anhydride eiüG ^ fills. The Nipchung wurc'c · P. Gtund s to 95 G ER-

11/12 31 ^{ßAD 0R] GINAL}

23U525

heats. and dam; ir. water comrades. Was he separated from a solid, do η ir. Aqueous Isoprnpanol u-Din nkristallisiert yield "ti Ajnid was 3 ^ 0 at a Gchinelzpunkt 154-1? ⁽⁰ H.

Elemontnnnnlyse:

calculated: G 78.35 II 10, 'HN 2.54! ^ veneer: U 7 ^, 33 H 1G ₁ ^ IM 2.57

Example 25

NZ ³ I ^ -DL (J ¹ , ^r '-di-t-butyl-4'-hydroxyphenyl) -J-

In ο in '; η With Tliei'inoiaeter, liührwork, Glaisen attachment with; The funnel and condenser on the three-necked flask with a volume of 1 liter were 50 ε (0.0? »- ^l - ^ 7 / d ^> yyyhenyl) -3-pentyl7-l · I-met; byla · lin., 20:! nl Triäthylnmin uir ¹ '." • CO cc of hexane dimer mixture were Iiühruru; 30 C stearoyl chloride r, u ^ eret ^ 't and 2 hours lan jf / ^ TÜhrt.

The triethylamine hydrochloride was separated by filtration and the hexane removed under ieduzierten pressure * The isolated material was solidified on standing and had a melting point of 79-02 ⁰ G.

8AD ORIGI _NAL 1/1231

IfO 23U525

Example 26

li- / i, 5-di (3 ', 5' -di-t-buty 1-4 '-hydroxyphenyl) -3-pentyl / -N-ributylacetamide

In one with a thermometer, stirrer and condensation cooler Reamed three-necked flasks of 500 ml 55.1 g (0.1 mol) Ν- / Ί, 5-di (3 ',?' -Cli-t-butyl-V-hydroxyphenyl) -3-pentyl7-N-n-butylamine, 250 ml acetic acid and 20 ml acetic anhydride filled. The Ilischunr, was under G hours Fiückl'l'luß cei; owed and chilled. The mixture was in Wasner poured, whereby a viscous oil separated. The oil was celöct in hot aqueous propanol and allow it to cool. The amide yield was 5%; the melting point lap; at 124 am 125 ° C.

Elementη! Analysis:

calc nc t: "GV ¹ 0.87 H 1Ü, G9 N-2.36 found: C 78.36 II 10.34 N 2.52

■ Example 27

N- / i, 5-di (3 ', 5'-di-t -butyl-4'-hydroxyphenyl) -3-pentiy-N-n-butyl-tenramide

In a three-necked flask with a capacity of 55.1 ζ C ° » ^{1 ο1} ) Ν- / Ϊ, 5-Di (3 ', 5'-di-t-butyl-4 ¹ -hydroxyphenyl) -3-f ppn-yl7-ll-n-butylamine, filled 30 ml of triethylamine and 500 ml of hexane. This

409811/1231

© AD OFJIG. '. VAL

23U525

31 C steaioyl chloride were added to the mixture with stirring. The mixture was stirred for a further 4 hours. ·

The trialhylamine hydrochloride was removed by filtration and the hexane is removed under reduced pressure. Of the The residue was dissolved in acetone to remove any stearic acid.

The liquid jacket was removed under reduced pressure and the amide clogging solidified on standing. The melting point la »5 boi 76 to 78 ⁰ G.

ßeirpiel ? _ '*>

Ν- / Ί, 5-di ( 3 ', 5 '-di-t-butyl-4'-hydroxyphenyl) -3-pentyl7-N-noctylacetamide

In one with a thermometer, stirrer and Kondenskühler designed from three-necked flask of 500 ml content wnrcinn 40 b (O, ÜG6 Hol) 1Ϊ- / Ί, 5-di (3 \ ^r j ^f -di-t-butyl - ^ '- hydroxyphenyl) 3-pGntyl7-lI-n-octylamine, C? eil iDsri ^ r.iureanhydrid and 2 ^ 'O ml Er? si [ ^T .räure poured in. The mix was ^! \ Hours to 90 ⁰ C heated. The mixture was poured into water and

29 separated an oily residue. Refractive index ^ q ^m 1 »513 ·

Bciryiel 2)

-/ Ϊ, 5-Di ( ⁷ J ' , T>' - <li-t-butyl-A -'- hydr jxyphonyl) -3-penty ^ -N-noctylstearnmid

40981 1/1231

In a three-necked bowl with a thermometer, stirrer and Clnisen attachment with dropping funnel and condenser. Flasks of 1 liter capacity were 40 .3 (ü, UGG Hol) Ν- / Ϊ _t 5-di (3 ', 5'-di-t-butyl-4' -liydroxyphenyl) -3-pentyl7-Un-octylamine, Filled in 20 ml of triethylamine and 400 ml of hexane. 21 stearoyl chloride was added to this solution with stirring, and the mixture was stirred for a further 2 hours.

The tri ^: iilylamine hydrochloride was removed by filtration and the hexane removed under reduced pressure. Dan Amid stiffened while standing; Melting point 71 to 73 ° C

example

H- / ^{5 l} , 5-di (5 l, ^r >'- di-t-butyl-4 ^l -hydroxyphcnyl) -3-penty] _i 7-N-noctadecyl acet?; Nid

In a three-neck flask with a ^{volume of Γ} 0 ml, equipped with a thermometer, stirrer and condenser, i \ Q g (ü, C ^ t Hol) Η- / Ί,? -Di (3 ', 5' -di-t-butyl ¹ -4-hydroxyphenyl) 3-penty ^ 7-LI-rl-octadecylamine, 2 ¹⁾ JSssigsäureanhydrid ml and 150 ml £ ssi ^ ^F: iure introduced. The solution was heated to 93> ° C. for 5 hours and then allowed to cool. It was poured into waeeer and a viscous residue was separated. The solvent was removed under reduced pressure. The Araid residue solidified on standing; Melting point 73 to 7 ° C.

BAD OR! G: NAL

409811/1231

Example 31

N / i, 5-Di (V, ^{r 'l} -di-t-butyl- ^/ i- ^l hydroxyphenyl) -3-pentyl7-N-Tl * - octadecylstenrami'l

50 g were placed in a boiling flask with a capacity of 500 ml (0.06? Mol) N- / i, 5-di (3 \ 5'-di-t-butyl-V-hydroxyphenyl) -3-penty \ 7-H-n-oc; tndecylamine, 20 ml of triethylemine and 250 ml of hexane filled. This mixture was 20.3 δ with stirring Stearoyl chloride added. The mixture was stirred for one hour. The trixthylamine hydrochloride was removed by filtration removed and the hexane stripped off under reduced pressure. The amide backbone solidified on standing; Melting point 53 to Gü ° G.

Example 32

N / i, 5-di (3 ', 5'-di-t -butyl-4'-hydroxyphenyl) -3-pentyl7-K -cyelohexylacctamide

25 g (0.043 mol) of N- / i, 5-di (3 ^l , 5 ^l -di-t-butyl-4'-hydroxyphenyl) - 3-pentyl7-H-cyclohexylamine, 25 ml. Eosic anhydride and 250 ml acetic acid are filled in. The Hirchuni ^ was heated to 95 ° C for 5 hours and then left to cool. The mixture was poured into water and a solid separated. After recrystallization from witchers resulted in an Amidauebeuto of 25 G with a melting point of Λ ^ Λ to

09811/1231 ^ßAD original

iffy 23AA525

Example 33

N- ^ ⁵ 1,5-di (3 ', Γ>' -di-t-butyl-4 '-hydroxyphenyl) -3-pentyl / -N-' -cyelohexylstearamide

25 ΰ (0.043 mol) W- _{i <} f!, 5-di (3 ^l , 5 ^l -di-t-butyl- ^ '-hydroxyphenyl) -3-pentyl7-N - ^{filled in c} y ^c lohexylamine, 20 ml triethylamine and 250 ml hexane. The mixture was stirred with 13 ^. E stearpyl chloride sucks. The mixture was stirred for one hour and the triethylamine hydrochloride was separated off by filtration. The hexane was removed under reduced pressure; Refractive index N ₁ ^ = 1.507.

Example 3 ^; <

N ₁ N '-M / i, 5-di (3 ¹ , 5' -di-t-butyl-4. -Hydroxyphenyl) -3-penty Ij- N, N'-dincetyl'ithylenediaiain

In a three-necked flask of 500 ml capacity equipped with a thermometer, stirrer and condenser, 12 g (0.012 mol) of Ii, N'-Di / l, 5-di (3 ', 5' -di-t- butyl-4'-hydroxyphenyl) -3-perjtyl7-ethylenediamine, 25 ml of acetic anhydride and 250 ml of acetic acid. The mixture was heated to 90 ° C. for 7.5 hours. The volume was reduced to 100 ml under reduced pressure and the mixture was allowed to cool., "N. The yield of amide was 10.5 G with a melting point of PAy to 24G ⁰ C.

_BATH

/ ♦ 09811/1231

Element analysis:

Calculated: G 78.49 H 10.25 N 2.54 Found: C 70.77 II 10.55 N 2.55 / 2.50

Example 55

N, 1Γ-di / i, 5-di (3 ', 5'-di-t-butyl-4 ¹ -hydroxyphenyl) -3-pentyl7-Ν, Ν'-disteaioylethylenediamine

30 G (0.029 Hol) N, N'-Di / i, 5-di- (3 ¹ , 5'-di -t-butyX-4 ¹ -hydroxyphenyl) -3-pentyl7-ethylenediamine, 20 ml of triethylamine and 400 ml of hexane. 10.2 ctearoyl chloride was added to this 1 * .schun ^ while stirring, and the mixture was stirred for 3½ hours. Dar triethylamine hydrochloride was separated by filtration and the hexane

29

stripped off under reduced pressure. Refractive index Ν « ^y « 1.5O8.

N, N '-Di / Ϊ, 5-c? i (3 ', 5' -di-t-bntyl-4 '-hydroxyphenyl) -3-pentyl7-Ν, Ν'-diacetylpropylenediamine

In one equipped with a thermometer, stirrer and condensate cooler Three-neck flasks of 500 ml content were 20 β (0.019 Hol) N, N'-Di / i, 5-di (3 ', 5'-di-t-butyl-V-hydroxyphenyl) -3-pentyl / propylenediamine, 25 ml of esniotic anhydride and Filled in 200 ml of acetic acid. The mixture was 3 hours

409811/1231

ift 23U525

heated to 95 C and left to cool. The mixture was poured into wascer and a solid separated. That' Amide melted at 100 to 10 ^ ° C and wop 17 lbs.

Example 57

N, N'-diacetylhexamethylenediamine

40 g (0.057 Hol) N, N'-Di / ^, 5-di (3 ', 5 ^f -di-t-biityl-4' -hydroxyphenyl) -3-pentyl / hexnaethylenecliamine, 25 ml Escir; acid anhydride and 200 ml _L .F ^: iure filled. The linchuti was heated to 95 ° C for 5 hours. It was then poured into water, with a strange residue separating off. The residue was driven off at 120.degree. C. under reduced pressure. The amide sintered at 95 to 100 ° C.

Leg play ^ o

N, N ¹ -ii / i, ^ - di (3 ', 5'-di-t-butyl-V-hydroxyphenyl) -5-pentyl7-NjN'-dimethylr.Mco.inaraid

32 ε Ν- / Ϊ, 7-di (3 ', 5' -di-tbutyl-4 ¹ - hydroxyphenyl) -J-pentylZ-li-rafithylajnin, 15 ml of triethylamine and 250 ml of hexane. This solution was

ORIGINAL BATHROOM 409811/1231

23U525

with stirring 'ι. 08 ο Amber acid chloride added. Then the Minc'mn ^; ^l \ Gt and en under reflux [boiled.

The Iroflult was separated off by filtration, washed with water and recrystallized from methanol. The product .schmölze at ΓΊ2 to ⁰

At ppi el 59 -.

1Ϊ- / Ϊ, 5-di (3 ',' .- '-di-t-butyl-4' -hydroxyphenyl) -3-pentyl / benzainide

In a three-necked flask with a capacity of f / 00 ml, fitted with a thermometer, stirrer and Claisen attachment with dropping funnel and condenser, were Ό, 5 c 1, H-Di (J ', 5'-di-t-butyl-4'- hydroxyphenyl) -3-pentylaaiin, 15 ml of triethylamine and 250 ml of benzene. 1 1/2 benzoyl chloride was added to this solution with stirring. Then the mixture was ¹ l GtuK'Jen under reflux cekocVit.

The triethylrunin hydrochloride was separated off by filtration and the benzene was zoced off under reduced pressure. The residue was dissolved in hot hexane. The benzamide separated niob bni cooling nb; Melting point 173 am 130 ⁰ C.

Example 40

1J_ / 1, 5-Di (3 ^f , ^r ; '-di-t-butyl- ^' -hydroy.yphenyl) -3-penty] 7-N -benzylnmin

In a R'ihrautnklave with 3.73 1 content were

1/1231 BADORiGtNAL

100 c 1 »5-di (ji ', 5' -di-t-butyl-4 '-hydroxyphenyl) pent anon-3, 25 g benayloruin, 12-10 ml isoproponol and 10 r 5'% 1'd / C filled. The Iiir.chunc, 4 to 3 hydrogen at ouf 5O ⁰ C for 4 hours under J ^1}. He, 0.175 Hol (87 %) of hydrogen was absorbed.

The catalyst was separated off by filtration and the Alcohol under reduced pressure from ^ ezo ^ on. The residue was Dissolved in hot hexane. On cooling, the benzylamine separated a; Melting point 125 to 127 ° G.

jppiel

Η- / Ί, 5-di (3 ', Γ ¹ -di-t-butyl-4. -Hydroxyphenyl) -3-penty 17-N-phenylamine

100 g 1,5-di (J. ', ^' - di-t-butyl - ^ '- hydroy.yphen-Dpentnnon- ?, 2G s aniline, 1P00 ml isopropanol -Ind 10 c 5% ld / C eincefüllt. The mixture was heated _2% l ^r) hours at 5O ° C and 1.75 hours under 35 to 40.5 Pt hydrogen to 100 ⁰ C. 0.14 moles (70 %) of hydrogen were absorbed.

The catalyst was separated off by filtration and the alcohol was removed under reduced pressure. The residue was solved in hot witches. When it cooled down, the area settled down; Melting point 122 to 123 ° C.

U 0 9 8 1 1/1 2 3 1

The folf /> ndo example gives details on how to make it a typical intermediate useful in the invention product mi.

example > \ 2

1, 5-UiC ⁷ ", ^r · '- ^ it-butyl - ^ -' -hydroxyphenyl) pnntadien-1, 4-one-3

In a three-neck flask with a capacity of 11, equipped with a thermometer, stirrer and gas supply tube with a condenser, 100 p * 3 "S'-di.-t-butyl - ^ - hydroxybenzaldehyde, 13 g acetone and 7 ⁾ 0 ral ir.opropanol filled. The mixture was cooled to 5 to 1 ° C for 3–5 hours in [; Chlorine waste gas was introduced. The reaction mixture was then poured into ice water and the product was separated off by filtration. The yield was 103 ε. This solid was encircled from 30% ethanol aqueous solution. It then had a melting point of 252 to 25'J ⁰ U.

Deirpiel ^ 3

Stabilization of polypropylene

The stabilizer (0.1 part by weight) was placed on a roller at 1G ^, 5 ⁰ O in 100 parts by weight Profax 6f5O1 (unstabilized folypropylene resin from Hercules: density 0.904; Schinelz flow index 4.0 g / lo min at 230 ° C - ASTM D-I238 This stabilized polypropylene was pressed with a Farrel press * to form 1.9 mm thick sheets, and buttons were then punched out of these sheets.

409811/1231

Buttons with 0.1 part stabilizer, 0.4 parts of DJlouryl 3,3'-thiodipropionate (DLTDP) in 100 parts Profax 6501 manufactured.

Three Unbind of each sample of the polymers were r.tabilirierten unp at 14O ⁰ G in a furnace with Luftumwäl ^; aged and the legend of embrittlement was recorded. The break point was the time in days after which the first sign of cracking or crumbling appeared in two out of three pieces.

Breaking point

only with stabilizer DLTDI

1,5-di (3 ', 5'-Ίi-t-butyl-4'-hydroxypbeny1) -

3-pentyl noetate 5

1,5-di (3 ', 5'-d i-t-butyl-4 · -hyd roxypheny1) -

3-pentylnioarate 14

1,5-di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -

, 5-di (V, 5 '-'U-t-butyl-4 · -hydroxyphenyl; -3-pentyl / succinate

Di / i, 5-di (V, ^r , '- di-t-butyl-A · -hydroxyphenyl) -3- ρ entyl / adip st

^ Q ¹ ^ ^{: l} -di-t-butyl-4 · -hydroxyphenyl 5 -3- ⁵ Pe η ty l / ph thai at

Di / i, 5-di (V, 5'-di-t-butyl-4 ¹ -hydroxyphenyl 5 -3-pcntyiyth iod ipropion at

Tri / i, 5-di (V, 5 ^f -di-t-butyl-4'-hydroxyphenyl) -5-pentyL / phosphite

17th 41 2C 53 1? 53 13th 53 27 2 ^q 13th BAD ORiGi:

40981 1/1231

Ν- / ΐ, 5-di (3 ', \ ^r - (I i -t-butyl-4' -hydroxyphenyl) -3-ponty] J ⁷ -Nn-butylaiain

Ν- / Ϊ, 5-di (3 ', 5'-di-t-butyl-4-hydroxyphenyl ) -3-pent, yl7-lI-n-oct3decyl main

Ν- / Ί, 5 - Ui (5 ', ^Γι ' -1 it-butyl-4 '-hydroxyphenyl) - ^7- pentyl / -II-cyclobexylamine

N, N '-Di / Ϊ, 5-d U 3', 5 '-di-t-butyl-4' -

hydi'oxypheny ^ - ^ - pentyl / ethylenediamine

Κ, Ν'-Μ / Ί, 5-U (5 ', 5' -di-t-butyl-4 '-

hydrnxyp> K; nyl) -3 ~ pe n ty! / propylenediamine

Ν- / Ί, 5-di (3 '» ^Γ " -Λ χ -t-butyl-4' -hydroxyphenyl) -3-P ^ ntyl / acetamide

Ν- / Ϊ, 5-di (3 ', ^r ; ·' -fii-t-butyl-4 '-hydroxyphenyl) -3-p ^f5 ntyl7stearamide

Ν- / Ί, ^r -Di (3 ', ^r -' -fli-t-butyl-4 '-hydroxyp} ionyl) -;> -p ^o ntyl7-N-methylacetnmid

N-Zi, 5-di (3'Λ'-di-t -butyl-4-hydroxyphenyl ) -3-p ^ utyl / -N-methylstearnmid

N- / 1,5-di (3 ', ^r >' -di-t-butyl-4 '-hydroxyphf? Nyl) -3-p on tyl / -Nn-butyl acetamide

Ν- / Ί, ^r ) -Di (3 ', ^r ' -di-t-butyl-4 '-hydroxy-' phr ny 1 ) - ^xL \> on tyl / -Nn-butyl st e or na id

Ν- / Ί, ^r -Di (3 ', ^r ·' -di-t-butyl-4 '-hyc mxyphenyl) -3-pontyl7-Nn-octylacetamide

Ν- / Ί, r-Di (3 ', 5'-di-t-butyl-4'-hydroxyphenyl ) -3-pctyl / -N-n-octyl stearainide

Κ- / Ί, 5-üi (3 ',! "- di-t-butyl-4' -hydroxyphenyl ) -3-pontyl / -N-n-octadecylacetamide

Ν- / Ί, 5-di (3 ', 5'-d i-t-butyl-4-hydroxy-

ptienyl) -3-pentyl / -N-n-octadecyl stearamide

Z.5 (3,5tylhydro3cy phenyl) -3-pentyl / -N-cyclohexylacetamide

N-Z "1, 5-di (3 ', 5' -di-t -butyl-4 '-hydroxyphenyl ) -3-pentyl / -N-cyclohexy is tearamide

1Ϊ, Ii '-Di / l ^r _? -di (3 ·, 5 '-di-t-butyl-4' -hydroxy-

phenyi; -3-pentyl _ / - N, li'-diacetylethylenediamine 14

40981 1/1231

12th 40 13th 40 13th 35 12th 40 12th 40 8th 42 13th 52 15th 48 16 63 21 62 17th 62 16 56 14th 52 13th 43 17th 42 13th 34 14th 50 14th 63 8AD ORIGINAL

N, H'-Di / i, 5-'H C3 ¹ , 5'-di-t-butyl-4'-hydroxyphenyl) -3-pen ty 17-N, N'-distearoylethylem'iainin. 9 69

IJ ₁ N'-Di / ~ 1,5-di (3 ^ 5'-di-t-butyl-4'-hydroxyphenyl) -3-pcntyl / -H, N'-diacety1-propylenediamine 29 G 9

N ₁ N '-ΰί / ί, 5-di (3', 5'-di-t-butyl-4 '-hydroxyphenyl) -5 ~ penty 1 / -N, N'-diacety! Hexamethylenediamine 22 56

auox 107 '■ * (<~ in commercial standard · Gt.obilira-

gate) 9 41

* -Uctodccyl-3- (3, ^ - di ~ t-butyl-4-hyclj ^- oxyphenyl) propionate

Under the same conditions, the breaking point for Irofnx 6 ^r ) ü1 plloine is less than 1 Ta ^ and for Profi? Κ 0 ^ 01, doc is immobilized with 0.4 parts DLTDF per 100 parts Profax G501, the breaking point is 12 Ta ^ e. The in the above Tn-bolle with Eorabirationen from the original Gt.nbilisntorri! and DLTDI 'rjezci ^ te r.3 / nerr "i. ^ tinche effect int hochFt boinerkonswert.

At ppi el ^l \ '\

tig of HochRchlaGfecteiü lOlyr- ^ yrol

The stabilizer (0.1 part) was on a roller mill at 149 ° G in 92 parts by weight of Styrene GG (unctabilized Polystyrene from Dow) and 0 part by weight of Diene 55 (in solution polymerized polybutadiene with a non-colored antioxidant from Firestone; Koonoy virosity: 50-60) a ^ erircht. üiecos ptabilized Polyf; tyrol was »with a

BATH

Farrel-Presoe pressed into 1.9 ram thick plates and then cut into 3B, 1 ram quad ¹ nth.

The same procedure was followed for samples with 0.1 part of a stabilizer and 0.2 part of tri (nonylphenyl) phosphite (Polygard).

The Q'indrates were at 93-3 CJ in an oven with air circulation ! '^ ages, and the days were determined that were required for their pre-yellowing. The number of days is indicated in the following table:

Days

only with stabilizer Polygard

1, 5-Üi (3 ', ^r >-di-t-butyl-4' -hydroxy-

phenyU - ^ - pentyl acetate - 60

1,5-di ( ⁷ j ', ri' - 'Ht-butyl-'»'-hydroxyphenyl) -3-pentyl stearate

Di / i, 5-rt i (3 ', ^r :' - (I i -t-butyl-4 '-hyrl rory-) 7di

, Γ'-di (V ,: «'-Ii -t-butyl -4'-hydroxyphenyl ) -3-pentyl / phthalate

Ν- / Ϊ, 5-di (3 ', 5'-di-t-bntyl-4 ¹ -hydroxyphenyl 5-3-pentyl / acetamide

N- / i, 5-di (V, 5'-di-t ^{-butyl-4 1} -hydroxyphenyl; -3-pentyl / etearamide

Ν- / Ϊ, 5-Di (V ₁ ^ ¹ -di-t-butyl-4-hydroxyphenyl 3-3-p en ty l / -N-me thy Iac et nnid

Ν- / Ί, ^v j - \) x (3 ', 5' -di-t-butyl-4 '-hydroxyphenyl) -3-pen ty 1.7-N-iüe thy Ir. te 3rara id

—— 60 20th 60 - 60 30th 50 30th 40 20th 70 20th 40 bad ntstni

40981 1/1231

23U525

Ν- / Ϊ, 5-Di (3 ', Γ ■' -di-t-buty1-4 -hydroxy-

phenyl) -3-p ⁿ nty] ₁ ZNn-butylacetamide 30 70

Ν- / Ϊ, 5-di (3 ', I ■' -di-t-butyl-4. -Hydroxyphenyl) -3-pentyl _J ZNn-butyletearamide 20 50

N- / 1,5-di (3 \ V-di-t-butyl-4'-hydroxy-

phenyl) -3-pentyl / -N-n-octyl acetamide ■ 20 50

N- / i, 5-Di (3 ', ^r »'-di-t-b'jtyl-4'-hydroxy-

phenyl) -3-pentylZ-N-n-octyisteararaid 20 50

Ν- / Ί, 5-di (3 ', ^r ; -d it-butyl-4-hydroxy-

pheny1) -3-penty 1Z-N-n-octadecylacetamide

Ν- / Ί, 5-di (3 ', 5'-di-t-butyl-4 -hyd rovy-

pnenyl) -3-pentylZ-N-n-octadecylGtfjnraraid

N- / i, 5-Di (3 ', 5'-di-t-buty1-4'-hydroryph e ny l) -3-p entyl_Z-N-cy c lohe xy! acetamide

20th 70 ΊΟ ίο ? 0 40 20th 50

Ν- / Ί, 5-ϋί (3 ', ^rl -di-t-buty 1- ^ 4' hydroxyphenyl) -3-p C "η t; yl / -lT-cyclnhexylr; teara: n in

H, N'-ui / i, 5-dJ (3 ^_l))? '-Di-t-butyl-4 ^I -hydioxyphenyl) -3-pf nty] J ^r -N, li' -distearoyläthylondianiin 10 70

N, N ¹ -Di / ΐ.5- ^ U3 *, 5'-di-t-butyl-4 ¹ -hydroxyphenyl) -3-pen ty I ₁ ZN, N '-diac e ty I propylenediamine 10 70

N, N'-Di / I, 5-di (3 ', 5'-di-t-butyl-4' hydroxyphenyl) -3 ~ yentyl / -N, N'-dineetylhcxa me thylend i ami n

2,6-di-t-butyl-p-crenol

107 ^r

10 50 20th 70 20th 50

Under the same conditions, the number of days required for the yellowing of unstabilized, high-impact polystyrene and of polystyrene stabilized with only 0.2 parts of Polygard was less than 1 and 3o, respectively. In this way, the synergism of the combination of inventive

ßAD ORIGINAL

409811/1231

£ ^? 23U525

according to Gtnbil! roten and Polycard, ^ ezeifjt.

Example ⁷ ^
Stabilizer !!: · from ElDII

Unstable EPDH (SB % ethylene; 32 % propylene; 10 / Ό ethyl idonnorbornnen; crund molar viscosity 2.3) was dissolved in an amount of 100 parts by weight in an excess of hexane. Diener solution were 0, ^ΐ Γ> Parts Gwibilisator iirid added the Lösun * was for dissolution of the stabilizer Shaken. Dar. Solvent was evaporated to obtain the stabilized polymer.

This stabilized polymer was then subjected to an oxygen absorption test; ^eni AESS the J. Ghelton in AGTH Gpecial r aining l'ublication 59 (March 2 ?, 1949) method described. This test determines the time necessary for the absorption of 20 ml of oxygen by 1 rj polymer. The minimum requirement to pass the test was 420 min.

Gtnbilizer Scit _T Hin.

1, 5-DiO ¹ , 5 '-di-t-buty 1-4'-hydroxyphenyl) -3-

pentyl benzoate> 420

, (, yyjpy) 3-pentyl / succinate > 420

Tri / ⁵ l, 5-tJi (3 ^l , "'- di-t-buty 1-4'-hydroxyphenyl) -3-pentyl7phosphite;

10? 6> 420

Empty attempt (no stabilizer) 230

40981 1/1231 ^ßAD Origjnal

-yf- ■

The effectiveness of the compounds according to the invention for Stabilization of elastomeric terpolymers made from ethylene, Propylene and non-conjugated diene were proven by this.

In summary , the invention is directed to 1,5-pi (3 ', 5'-dihydro c * rbyl-4 ' -hydroxyphenyl) pentyl derivatives, including the 3-pentyl ester, amine and amide compounds. It also relates to the stabilization of organics by the inclusion of these derivatives, either alone or in combination with a dialkyl 3,3'-thiodipropionate or a tri (alkaryl) phosphite.

11/12

Claims (1)

- 5 * claims where the following meaning applies: R and H ¹ are each hydrogen or alkyl with up to 4 carbon atoms or together, including the carbon atom to which A is attached, form a carbocyclic ring with 5 to 7 carbon atoms; P 5 R to R are hydrogen, alkyl, cycloalkyl, aryl, aralkyl or alkaryl, of which each of these hydrocarbon groups has up to 12 carbon atoms and where, when A has the meaning -OH or = »0, U and R ¹ only Hydrogen or alkyl and at least two groups of IV ~ to IK hydrocarbons with at least each J are carbon atoms; q A is -OH, -CR ^G , -OR ⁷ , = 0, * N, = N-ii ⁷ , 10, », ΓΌ.-, R ^G -CO-, G
rC R -N-R ', -CC-ir-C-Ü-, or R' -NR ^J -II-u '; C. int R °, ϋ "-0- or R -S ^ /, 0981 1/1231 bath R ° and R ° are. Hydrogen, alkyl with up to 30 carbon atoms, cycloalkyl miL. ⁷ j> bin 7 carbon atoms, aryl, aral>; yl, alkaryl, hydroxyalkyl, alkoxyalkyl, alkylaminoalkyl or alkylthioalkyl, where the last seven radical bins can each have 16 carbon atoms; Ii and ii 'can be used together with the nitrogen with which they are connected in ß "-N-il 'r.ind form a lterocyclinic fissure; q
Ir is alkylon, oxydialkylene, thiodialkylene or arylene with each up to 1f. Atoms; m is 1 if A by a simple bond to the rjloichmrentylkohlenntoffatoia hür. ^ t, and it is int zero if A by a r-ine double bond to the same lcntylkohlenrtoffatoia h "dn [-t; and η is a canae number corresponding to the functionality of A, with the exception that en 1 irt when A is separated by a double bond jrrj on three of the same fentyl carbon content 2. Compounds according to claim 1, characterized in that that u »is 1. 3 connections according to claim 1, characterized in that that η * 2. ^l \. Connections according to claim 1, characterized in that 0 GO that A R ° -C-O- or -OC-R ^ -C-C- b »doi-tet. BATH ORIGINAL 409811/1231 >. Vei! »Indungen according to claim 1, hand-marked, that A R -'- V.-li? odor R ^ K-lp-li-U ⁷ bodoutot and K? Y / ancerstcff π "
or RO- int. 6. Compounds according to AnnpruCh 1, characterized in that R and R ¹ ' ¹ each meaning of hydrogen, Ir to R- the Meaning of t-butyl, A the meaning of R'-N-ii ^ -N-R ', 7 p Il η R 'have the Dedeutv.nij of R ^ -O-, IV ^J dip meaning of alkyl and R ^{y is} alkylcn and η is »2. 7. Vorbiii ' ¹ ün ^ en according to claim 1, characterized in that dnß R and R 'hydrogen, R ^{2 to} R ⁵ t-butyl, AR ⁶ -NR ⁷ , R ^G denotes alkyl, R ' ⁷ ii ^G -G-, R ⁸ denotes alkyl and η »1. 8. Vorbiriilun ^ s still claim 1, characterized in that if R and R ^{1 are} hydrogen, R ² to ] £ ^? t-butyl,
Ü AR ^J -GO-, ir alkyl and η - 1 mean. '). Connections according to claim 1, characterized in that that R and R 'are hydrogen, R ² is H ^ t-butyl.
O Ü A -ü-C-fi ^ -CC and η - 2 mean. 10. H, H ^l -Di / ^, ^r . -Di (3 ^l , 5'-di-t-butyl-4'-hydroxyphenyl) -3-pentyl / -N, IJ-ilii-, teoroylethylenedia: nin. BAD ORfGINAL
409311/123 1 11. H.N ' pentyl / -N, N'-diacetylpropylenediamine. 12. U, IV -di / 1,5-di (3 *, T '' -di-t-butyl-4 '-hydroxy _P henyl) -3-pentyl / -N, N'-diacetyläthylendiamin. ' 13. Ν- / Ϊ, ^r -Di (3 ^l , 5'-di-t-bijtyl-4'-hydroxyphenyl) -3- ' ^: pentyl ^ -N-methylstearomide. 1 ^ · ür'janiGchcs Ilaterial, dao duich Linffektun; j; erf of air, heat or light ^degradation: üut, characterized in that it liaß a ^ to protect this deterioration food wirksonc Men ^ e a compound of formula HO - is added, where Ii to H ¹ , A, m and η have the meanings indicated in the claim. SAD 811/12 3 ίή 23U525 1G. Material according to approach 1S>, characterized in that it contains a ^ ura protection kO £ en the Vnx-rchlochterung effective men ^ el) inll: yl-3, 3'-thiodipropionst,. in which the alkyl group η · "· have up to 20 carbon atoms. 17 material according to claim 16, characterized in that that the material is polypropylene. 13. Hatorial according to claim 17, characterized in that that the thiodipropionate is dilauryl-3,3'-thiodipropionate. 1'?. Material according to 'claim 13, characterized'-ekenn;; eic) met, f ⁿ aß dio cheiuirche compound H, N'-Di / i, Γ-di (3 ', * 3'-di-t-butyl-4 ^l -hydroxy [^ henyl) -3-pentyl7-N, N'-distonroylethylenediamine is. 20. Material according to claim 13, dPdurcli .-. E ^ enn that the veri.-i ndunn K, IV -Di / i, 5-ci (3 ', 5' -di-t-ünty 1-4 '-hydroxyphenyl) -3-per.ty \ 7-li, N' -diacei.yIpropy 1 endia ^r ain i st. 21. Ilatorinl according to claim 18, characterized in that the chemical compound- N, N'-Di / ί, 5 ^ di (3 ', 5'-di-t-butyl-4 ^l -hydroxynhenyl) -3-pentyl7- Is N, N'-dincotylethylendianine, 22. Material according to claim 13, characterized in that the chemirchr · Vcibindunj; Ν- / Ί, fi-Di (3 ', ' j '-cU-tb ^ hydrox3>' phetiyl) "3-r ^oni yi7-II-netby] stoprnnid int. 1/1231 23U525 23 · Mni.erifll nnch claim ίο, ^ .tTl-icIj? ^: ; ok indicates that the chemical compound N - / "1,5 / -Di (3 ', ^' - ^ it-bjtyl - ^ '- byd ι oyyphcnyl) -3 ~ pei) fcyl / -ll-n-butylacr -t3 ⁱ : n '* int. 2 '\. Material according to. ^f ; p- _L i 15, characterized ^ denotes that it contains a v; ii * ks? iino men ^ o Ti-iar-ylphosphite, in which each aryl ^ ruppe an odei ^ v, ei alkyl groups with woni .ptens Contains 8 carbon atoms. 25 material according to claim 2 ^, characterized in that The oi ': nnir.che material' polystyrene irt. 20. llatfjriel according to claim 2 ^r > , dnclur.h ^r 'e! CentK'eichnot that the Γΐιορρηϊτ is tri (nonylphenyl) phthalate. 2V '. Material still claim 26, d / idnrc'o "je ^ onn. '. Eichnet, that the chemical compound Ν- / Ί, 5-Di (3 ', 5' - ^ i-thydroxyphenyl) -3-pentyl / -N-inethylaceta.: iid i. «3t. 2- ^r j. ilotei'ial na ^ h claim 2G, iodu ch marked, that the chemical compound Ν- / Ϊ, 5-Di (3 ', 5'-iU-t-butyl-4 · - hydI · oxyphenyl) -3-pentyl · 7-N-n-butylacetaiflid int. 29 · Material according to claim 2G, characterized in that the chemical compound Ν- / Ί, 5> -Di (3 ', V-di-t-butyl-V-hydroxyphenyl) -3-penty], / - ii-n -octac] ecylacetassiid is. BATH I OO P 1 1/1 "^ ' 30. Material according to claim 2G, characterized in that the chemical compound 11,11 '-Di / ΐ, 5-di (3'>5'-di-t-butyl-4'-hydroxyphynyl) -3-penty] J ⁷ -N, N ^l -diGteafOyläthylen'Uamin is. 31. Material according to claim 26, characterized in that the chemical compound N, ll'-di / "1, ^l 3-di (3 ^l , 5'-di-t-butyl-4 ^l -hydroyyphnnyl) -3-penty ] _v / -N, N'-diacety! propylenediamine. 32. Material according to claim 15 »characterized in that that represents organic material from an elastomeric terpolymer Ethylene-propylene-non-conjugated diene ir-t. 33- Hnterial according to claim 24, characterized in that c that the oi'fjanic materini is a high-strength l'olystyrene int. 409811/1231 BAD OR! S; ?? AL