DE2008464A1 - New azole compounds, processes for their preparation and their use - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

200846 A-

Case 6683 / E / R.

Germany

New azo compounds ·, processes for their preparation and

their use.

The invention relates to new azole compounds, Process for their production and their use as antioxidants for organic material that

00 9 8 37/2273

normally subject to damage or destruction due to oxidative influence.

The new compounds correspond to the formula

corresponded, wherein R is a hydrogen atom, an alkyl radical with 1 to 12 carbon atoms, a cyanoalkyl radical with 2 to 4 carbon atoms, an alkoxy radical with 1 to 4 Carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to 4 carbon atoms in the alkyl part, a trifluoromethyl radical, a halogen atom or a group - (CHp) -CO-E, in which E is a hydroxyl group, an alkoxy group with 1 to 18 carbon atoms, one optionally substituted alkylamino radical with 1 to 18 carbon atoms, one optionally substituted hydrazine or a morpholine radical and ρ corresponds to 0, 1 or 2, η an integer of 1 to 3, X, an oxygen atom, a sulfur atom, an -NH- or -NQ, - grouping, Q, an alkyl radical of 1 to 18 carbon atoms, Y, a branched alkyl radical. with 1 to 4 carbon atoms and Z, one hydrogen atom or one mean branched alkyl radical with 1 to 4 carbon atoms.

The preferred halogen is chlorine. Compounds with particularly valuable properties are those of the formula

009837/2273

wherein Rl is a hydrogen atom or an alkyl group with 1 to 12 carbon atoms, Rg is a hydrogen atom, an alkyl group with 1 to 12, preferably 1 to 4 carbon atoms, a cyanoalkyl group with 2 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a phenyl group , a phenylalkyl radical with 1 to 4 i

Carbon atoms in the alkyl part, a halogen atom, preferably a chlorine atom, or a group (CHg) -CO-E ₁ , -. wherein E _{1 is} a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, an alkylamino group having 1 to 18 carbon atoms or a morpholino group and ρ is an integer 0, 1 or 2, m is the integer 1 or 2 and X _{1 is} an oxygen atom Mean sulfur atom or an -NH- group, and

wherein R _{1 is} a hydrogen atom or an alkyl radical with 1 to 12 carbon atoms, Rp is a hydrogen atom, an alkoxy radical with 1 to 4 carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to 4 carbon atoms in the alkyl, a trifluoromethyl

009837/2273.

rest or a halogen st-om, ™> the number 1 or 2,

BATH

2008484

X is an oxygen atom, a sulfur atom, an -NH- or -NQ ₁ - group and Q _{1 is} an alkyl radical having 1 to 18 carbon atoms.

Further compounds with valuable properties correspond to the formulas

wherein R, has the meaning given above and R, a hydrogen atom, a cyanoalkyl radical having 2 to 4 carbon atoms, an alkoxy radical having 1 to 4 carbon atoms ,. a phenyl radical, a phenylalkyl radical with 1 to 4 carbon atoms in the alkyl part, a trifluoromethyl radical, a halogen atom or a group - (CH ₂ ) -CO-E, where E is a hydroxyl group, an alkoxy group with 1 to 18 carbon atoms, an optionally substituted alkylamino radical with 1 to 18 carbon atoms, a possibly substituted hydrazine or a morpholine radical and ρ corresponds to 0, 1 or 2, and m is the integer 1 or 2.

009837/2273

200846A

R. _Λ 4 \ O

(5) ^ ^Ν

K N

wherein TU is a straight or branched alkyl radical with 1 to 12 carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to 4 carbon atoms in the alkyl part, a halogen atom or a group - (CHp) -CO-E, in which '% E is a hydroxyl group, an alkoxy group with 1 to 18 carbon atoms, an optionally substituted alkylamino radical having 1 to 18 carbon atoms, a
optionally substituted hydrazine or a morpholine radical and ρ corresponds to 0, 1 or 2, and R, - is a hydrogen atom or, if R ^ is a. Alkyl radical means
also denotes an unbranched or branched alkyl radical having 1 to 12 carbon atoms.

P (GH ₃ ) ₃
(6)

wherein R ^ is a straight or branched alkyl radical with 1 to 12 carbon atoms, a phenyl radical, a

009837/2273 '' "" '.

Phenylalkyl radical with 1 to 4 carbon atoms in the alkyl part, a chlorine atom, a hydrogen atom or a group - (CH ₂ ) -CO-E, in which E denotes a hydroxyl group, an alkoxy group with 1 to 18 carbon atoms, an alkylamino radical with 1 to 18 carbon atoms, a morpholino _{radical and P 1} corresponds to 0 or 2, and R 'represents a hydrogen atom or, if R ^ represents an alkyl radical, also represents an unbranched or branched alkyl radical having 1 to h carbon atoms.

V °

(τ) QT

where Rg and R "jev / eils an unbranched or branched one Means an alkyl radical having 1 to 12 carbon atoms and R, - preferably in the β or positions 7 of the benzene ring is.

, The compounds defined above can be produce according to methods known per se. The compounds according to one of the formulas (1) to (7) are obtained if an aldehyde or an acid, or acid derivatives such as acid chlorides, 'esters / amides or nitriles with the corresponding ο-substituted mono- or bicyclic aromatics.

Compounds of the formula (I) are obtained, intly

a compound of the formula

009837/2273

(8th) . ₂₂ ^

wherein B is a carboxyl group or that derived therefrom Means carboxylic acid chloride, carbonamide, nitrile, carboxylic acid ester or aldehyde group with an o-aminoaryl compound the formula *

X ₂ H

wherein R and η have the meaning given above and X, an oxygen atom, a sulfur atom, an -NQp- group and Q _{2 is} a hydrogen atom or a lower alkyl radical, by heating under a nitrogen atmosphere sphere in a melt or in the presence of a solvent inert towards the reactants, if necessary using a water elimination catalyst, at temperatures of 100 to 250 C to react, and the remainder Q ,, insofar as it differs from Q ₂ , by subsequent reaction in introduces the molecule.

009837/227 3

Compounds of the formula (2) are obtained in dan a compound of the formula

wherein B is a carboxyl group or that derived therefrom
Carboxylic acid chloride, carbonamide, nitrile, carboxylic acid or aldehyde group means with an o-aminoaryl compound of the formula

where R ₁ ', R', m and X ₁ 'have the meaning given, by heating under a nitrogen atmosphere' in a melt or in the presence of a solvent inert to the reactants, optionally using a dehydrating catalyst, at temperatures from 100 to 250 ° C to react.

009837/2273

Compounds of formula (5) are obtained by a compound of the formula (IQ) with an o-aminoaryl. compound the formula '

^X 2 ^H

in which R ₁ , R ₂ and m have the meaning given above and Xp is an oxygen atom, a sulfur atom or an -NQp group and Q _? means a hydrogen atom or a lower alkyl radical, by heating under a nitrogen atmosphere in a melt or in the presence of a solvent inert to the reactants, optionally using a water elimination catalyst, at temperatures from 100 to 250 ° C to react and the remainder Q ,, insofar as it differs from Qp, is introduced into the molecule by subsequent conversion.

Compounds of formula (4), (5) and (6) obtained one by making a compound of formula (10). with a o-aminophenol compound of the formula

009837/2273

or the formula or the formula

- 10 -

R ₅ HH ₂

wherein R ,, R, and m or R ₂ , and R, or Rl and R 'have the meaning given above, by heating under a nitrogen atmosphere in a melt or in the presence of a solvent inert to the reactants, optionally using a Dehydration catalyst, at temperatures of 100 to 250 ° C for the reaction

brings. . "

By reaction with o-phenylenediamines one obtains in this way

Benzomidazoles, while the o-aminophenols and the o-aminothiophenols the corresponding benzoxazoles or benzothiazoles result.

Can be summarized in a PLeaktiojisÄl ^ iciiung

one these reactions like fu) e ~ t- darsfeller>:

(9) R ₀ CH ₂ CH ₂ CHO

R ₀ CH ₂ CH ₂ COOH X ₂ HR ₀ CH ₂ CH ₂ COCl

R ₀ CH ₂ GH ₂ COE ₂

NH ₂

R ₀ CH ₂ CH ₂ CN

Here, Xp denotes an oxygen atom, a sulfur atom or an -Il-Qp group, Q ₂ denotes a hydrogen atom or a lower alkyl group, R denotes a phenyl radical which contains a hydroxyl group in the p-position to the ethylene group and also in the 5- and 5-positions carries the substituents Y ₁ and Z ₁ , which have the meanings given above, and Ep is an alkoxy radical.

For the imidazole compounds with the -N-Qp group in which Q _{p is} not a hydrogen atom, phenylenediamines with a primary and a secondary amino group are used as starting compounds. The sub- stituent g on the secondary nitrogen atom is a low molecular weight radical such as an alkyl group having 1 to h carbon atoms. All other residues Q, as defined above, foci subsequently introduced into the benzimidazole molecule by known methods.

The substituents R in the above reaction scheme have the meaning defined above and are, if η is 1, preferably in the ^ 'position, if η is 2 or »3 *, additionally-in 6- and 7-places

Ö0983772273

2008A6A

development of the benzazole residue.

The azoles are now prepared in accordance with the above equation, preferably by heating the two components in a nitrogen atmosphere to temperatures of 100 to 250.degree. C. In the absence of solvents, that is, in a melt or
work in the presence of organic solvents which are inert to the reactants and have a high boiling point. Acids such as boric acid can be used as a catalyst for the elimination of water and the ring closure reaction.

The water formed during the reaction is continuously distilled off from the reaction mixture.

Compounds which have a carbalkoxy or a carbonamide substituent in the benzene ring of the azole part, preferably in the benzene ring of the benzoxazole part, can also be produced by free carboxyl groups containing compounds of the formula (I), for example the compound of the formula

HOOC ^M C (CH) _

009837/2273

where R, and m have the meaning given above, esterified and this ester or the corresponding acid chloride with the corresponding amines, hydrazines or
Morpholinen converts.

Another possibility is that
introducing subsequently in an azole of formula (I) is a carbalkoxy or even bonamidgruppe "This method is advantageously applied to the in an oxazole eg

- ■■ - ■■ ■■ -. ■■ "■ · - - ·; '■. ■. I

Formula *

wherein R, and m have the meaning given above, the

Group .- (CHg) -CO-E to introduce, in which ρ is 2 and E has the meaning given above by doing the oxazole with an acrylic acid amide or an acrylic acid ester | sets and so, possibly through a further reaction stage, the desired substituents in the benzene ring of the benzene

oxazole part. .

Compounds of the formula are obtained in this way

· ■ "'" · "■'"'' ■ "" ■■■ '■''- -t *% tr- P, fi

00 9837/2273

R, a hydrogen atom or an alkyl radical old 1 to 12 carbon atoms, Rg a -CO-EU- group, in which E, an alkoxy group with 1 to 18 carbon atoms, an NHp group, an optionally substituted alkyl amino radical with 1 to 15 carbon atoms, a optionally substituted hydrazine or a morpholine radical, and m denotes the integer 1 or 2 by a compound of the formula

. G-OC

(19) (ν \

wherein R and m have the meaning given above and G corresponds to a hydroxyl group, an alkoxy group with 1 or 2 carbon atoms or a chlorine atom, with an alkanol with 1 to 18 carbon atoms, with ammonia, an optionally substituted alkylamine with 1 to

18 carbon atoms, an optionally substituted hydrazine or morpholine reactsj and compounds of the formula - - _; /

009837/2273

"In the

wherein R is a hydrogen atom or an alkyl radical having 1 to 12 carbon atoms, Rg is a -CHpCH ₂ -CO-E., - group, wherein E is an alkoxy group having 1 to 18 carbon atoms, an NHp group, an optionally substituted alkylamino radical having 1 to 18 carbon atoms, an optionally substituted hydrazine "or a morpholine radical, and m denotes the integer 1 or 2 by a compound of the formula

wherein R- and m have the meaning given above, reacts with acrylamide or an acrylic ester and the propion Srlureesterderivat further reacted with an alkanol with 1 to 18 carbon atoms, one optionally sub- -. substituted alkylarain with 1 to 18 carbon atoms, an optionally substituted hydrazine or! - orpholin.

The new connection points described valuable antioxidants, i.e. they are suitable for stabilizing organic materials against oxydafcive

009837/2273

Decomposition, such as by light-induced Oxidations or thermally accelerated oxidations. As materials that can be protected come in Consideration:

Homopolymers and copolymers of ethylenically unsaturated compounds such as vinyl chloride, vinylidene chloride, styrene, butadiene, isoprene, ethylene, propylene, acrylic and methacrylic acid derivatives, for example acrylic acid alkyl esters, acrylic acid amides and acrylonitrile; Polyamides, for example from G- caprolactam or from adipic acid and a diamine, polyesters such as terephthalic acid glycol polyester; natural and synthetic rubbers; Lubricating oils; Gasoline; vegetable and animal oils and fats; Waxes; Cellulose and cellulose derivatives such as cellulose esters.

For a good antioxidant effect, 0.01 to 5% of the compounds according to the invention are sufficient, based on that protective substrate, generally made of. The antioxidants can be used alone or together in the materials to be protected with other additives, such as plasticizers, pigments, light stabilizers, optical brighteners, with or can be incorporated without the aid of solvents.

The good stabilizing effect of the new compounds shows up e.g. under accelerated aging conditions at temperatures above 100 ° C. One of these conditions subjected to polypropylene, which is an antioxidant

009837/2273

holds * violated only after a much longer period of time showing signs of a Discoloration or a build-up of the material., matched with a stabilizer-free polypropylene * In the following examples, not otherwise indicated, the parts mean parts by weight and the. Percentages by weight, The melting points of the new compounds are not corrected ?.

009837/2273

example 1

29.24 parts of the compound of formula

²² ) H-COOC-CH _o -0H _o CS 3 2 2 ^N - <

(made from 2,6-di-tert-butylphenol and methyl acrylate in tert-butanol with potassium tert-butyl lat as a catalyst), 10.9 parts of ο-aminophenol and 5 parts of boric acid are melted together at 150 ° C., then heated under a nitrogen atmosphere (bath temperature 225 C) until condensation is restored. Oxazole is used with elimination of methanol and water. The resulting mixture of methanol and V / ater v / ill be removed through a descending condenser from the reaction mixture, Mach reaching the condensation temperature is stirred while still h hours at this temperature. 32 parts of light brown remain as the crude product. Oil that crystallizes on cooling.

To purify the crude product, it is chromatographed on aluminum oxide of activity I. The benzene eluates give 30 parts of the compound of formula

009837/2273

(23.)

Make it unique. Recrystallization from hexane melts that

Analysis product at 104 to 105 ° C.

Analysis:

Calculated: C 78.59 H 8.32 N 3.99 Found: C 78.36 H 8.35 N 3.90.

The following are produced in an analogous manner:

00 98 37/2273

ε L ζ ζ ι L ε 8 6 ο ο

Formula-
No." S. Antioxidants '3 y y f ~ \ TX Melting point
in 0 c 75 - 155 C. analysis H 7.95 calculated
found Ν 3.17 / ^(0H 3 UxI C. 75.16 H 8.00 N 3.81 (24) N CH ₂ -CH ₂ - ^^ 3-OH 153 - 75.25 N 3.59 N 3.14 NH 3> 3 C (OH-), 193 C. H 8.63 I Il ^ ~ 95 - 78.81 N 7.99 (25) -CH ₀ -CH ₀ -C 3 -OH -OH 192 - C. H 8.75 ^ C CH ^; 78.94 N 7.69 C (CH ₃ ) ₃ 76 C. H 9 ', 92 / \ .x ^ C- 80.45 N 2.93 (26) ^ ^ - 2 2 ~ ^ == <~~ C. H N \ _Q 80.70 10.04 N 3.00 96 C. H A. 81.59 7.99 (27) I CH3H _O -CH _O - <L3- C. H ² TI> 81.33 7.93

CD CD OO

tLlZ / LZBSQQ

formula

-No.

Antioxidants

Melting point
in ⁰ C

Analysis:

calculated found

^H 3?

^ C (CH)

for VCH ₂ -CH ₂ - ^^

124-125

C 79.11, H 8.76 N 3.69 C 79.40 H 8.77 N 3.59

H ₅ O '

^ C-CH -CH - <_> -OH

2 - <

"132-134

C 79.11 H 8.76 IT 3.69 C 78.90 H 8.99 N 3.58

(30)

C-CH -CH

C (CH)

• ζ. ι Χ

132-133

C 81.46 H 7.78 IT 3.28 C 81.23 H 7.84 • N 3.37

C (CH ")

- ^ I ■ C — CH _o -CH _o -t <_ ^

IQ3 - 104

C 81.46 H 7.78 N 3.28 cf '81.27 H 7.94 H 3.37

CD CD OO

ε Li ζ ι L ε 86 ο ο

formula

(32)

(33)

(35)

Antioxidants

C-CH ₀ -CH

Melting point in ⁰ C

104-105

118-119

113-114

B.p. 0.01 nm 200

Analysis:

calculated geiunden

C 71.58 E 7.31 C 71.43

7.31

3, € 3 3.57

C 78.86 H 8.55 N 3.84 C 78.78 H 3.47 N 3.85

C 78.86 E 8.55 N 3.84 C 78.91 H 8.44 K 3.92

C 80.87 K 10.28 K 2.69 C 80.81 H 10.52 K 2.85

O O OO

CO

tLlZ / LZQQQQ

formula

No.

(36) (37) (38) (39)

Antioxidants

(OHj) ₃ O

Q (CH ₃ ),

N = C CH ₂ CH ₂

Melting point in ⁰ C

94-99

131 - 1 ^ 2

109 - HO

119-120

Analysis:

calculated found

C 79.34 H 8.96 N 3.56 C 79.50 H 8.88 N 3.59

C 80.29 H 9.78 N 3.02 C 80.55 H 9.78 N 3.08

C 80.45 9.92 N 2.93 0 80.57 H 9.97 N 2.97

C 77.19 H 7.97. N 6.93 C 76, 91 H 7.71 N 6.80

O O CD

cn

formula
No. H Antioxidants C (CH) Melting point
in ⁰ C 166 - C. analysis H calculated
found 9.32 N 3.32 / YY ·· ( ntj \ Π- -OH C. 79.76 H 9.43 N 3.22 (40) \\ jii.y j ~ \ j "Vk // 2 2 ~ ^ --ς
N C (CH) 154 - C. 80.06 H 9.15 N 3.44 Q / YY -OH C. 79.56 H 8.99 N 3.46 (41) 118 - C. H 9.78 N 3.02 HC
I. "Vk // 2 ² ~ ^ --N C. 79.37 H 9.74 N 3.07 HCCH,
J I < H ₃ C 0 € ^ -oh 80.29 (42)
ι I. C (CH ₃ J ₃ 80.50 I ^iN - 168 * - 155 - 119

CD CD OO

ZLZZ /

Formula No.

Antioxidants

Melting point in ⁰ C

analysis

.!calculated
found

(43)

G 81.83 H 8.37 N 2.98 G 81.70 H 8.60 N 3.07

(44). ^CH 3 °

101 decomposition

G 75.56 H 8.19 N 3.67 "C 75.61 H 8.05 B 3 * 67

G (GH,)

101-102

G 74.11 H 8.06 .. N 3.20

G 74.31 H 8.21, K 3 ^ 14

Example 2

8.9 parts of the compound of formula

(46) ClOC-GH-CH

(prepared from the corresponding acid by boiling with an excess of thionyl chloride) v / earth dissolved in 20 parts of methylene chloride. This solution is added dropwise with stirring to a solution of 3Λ parts of o-amino-p-carbethoxyphenol and 5 parts of triethylamine in 100 parts of methylene chloride over the course of 10 minutes. The mixture is then stirred at reflux temperature (40 ° C.) for 8 hours. To remove the triethylamine hydrochloride formed, the reaction solution is shaken out with water, the methylene chloride extracts are dried and the methylene chloride is then evaporated off. 3 parts of boric acid are added to the dry residue and the entire reaction mixture is heated to a bath temperature of 250 ° C. under a nitrogen atmosphere and stirred at this temperature for K hours while distilling off the water formed. 10 parts of yellow-brown oil are obtained.

009837/2273

To purify the crude product, it is chromatographed on silica gel. The benzene extracts result in the compound of the formula "

(47)

CH .-- O0C

Melting point: 103 to 104 "° C.

Analysis:

calculated: found:

C, 73.73, H 7.85 -, · ;. C 73.57 H 7.82

The following are produced in an analogous manner:

Ά 3.31 N 3.42

CH-OOC

(48) _n " _nnn _tU C-CH ₂ -CH ₂

.O

Melting point: 92 to 94 ° C

Analysis: bereclinet: C 74.11 found: C, 74.31

H 8.06 N 3.20 H 8.21 N 3.14.

98'37 / 2

Example 3

5 parts of the compound of formula

(48) ηυ - ^ =? - υη _ο υη «, υ_ ivj — rjQOÖH

are dissolved in 30 parts of methyl alcohol. A solution of 1.5 parts of potassium hydroxide in 10 parts of water and 50 parts of methyl alcohol is added. The reaction mixture obtained is stirred at reflux temperature for 1 hour. It is then diluted with 200 ml of water, the reaction solution is cooled with ice and acidified with concentrated sulfuric acid. The crystals which precipitate are filtered off with suction, washed with water and dried in vacuo.
Yield: 4.1 parts.

After recrystallization from acetone / water and methylene chloride / hexane with simultaneous decolouration with fuller's earth, the analytically pure compound of the formula

009837/2273

obtain.

Melting point: 241 to 242 ° C

Analysis: Calculated: C 72.88 H 7.39 N 3.54

Found: C 72.77 H 7.24 "N 3.56.

The following is produced in an analogous manner:

^ ⁵⁰ ^ HD - <^> - CHpCHpC ^ J [J CH ₂ CH ₂ COOH .. {H ₃ O 1

(CH ₅ ) ₃ C

Melting point: 60 ° C decomposition

Analysis: Calculated -: G 72.19 H 7.92 N 3.24 Found: C 72.78 H 7.87 N 3.21

Example 4 '

4.1 parts of the compound of formula

009837/2273

0.1 part of sodium ethylate and 20 parts of octadecyl alcohol are under nitrogen for 3 hours at 1.40 ° C stirred. The excess octadecyl alcohol is then removed in a water jet vacuum at a bath temperature of 200 ° C distilled off. 5.2 parts of the compound of the formula remain in the reaction flask

(51)

Melts after two recrystallization from methanol the analysis product at 57 to 58 C.

Analysis: Calculated: C 77.85, H 10.11 N 2, 16 Found ■: C 77.98 H 10.17 N 2.28.

The following are produced in an analogous manner:

(CH) ₃ C _n

(CH ₃ ) ^ C

^H 2 ^CH 2 ^C xx JL

^Xf z. ' γ

Melting point:
Analysis:

56 to 58 ° C

calculated: found;

C 78.17 H 10.29 N 2.07 C 77.98 H 10.34 N 2.00.

009837/2273

example

4.37 parts of the compound of formula

(45)

™ COOOH

and 1.3 parts of octylamine are for 8 hours at a Bath temperature of 150 ° C melted together and stirred. It is then cooled, the reaction product in methylene chloride taken up, boiled with fuller's earth to decolorize and, after separating the fuller's earth, the solvent evaporated. 4.4 parts of a yellow-brown oil are obtained, which slowly crystallizes. For cleaning is recrystallized from hexane and acetone / water.

The analysis product has the formula

Melting point: 92 to 93 ° C ...,,. ^,

Analysis: Calculated: C, 76.36, H ^: 9.42, N, 5.24

* Found: C 76.06 H 9.53 N 5.43.

009837/2273

The following are produced in an analogous manner:

(54) HO - ^^ - C

LC ^N

Melting point: 58 to 59 ° 0.

Analysis: Calculated: C, 78.29, H, 10.45, N, 4.15 Found: C, 78.09, H, 10.20, N, 4.19

(55) HO-C3-OH ₂ CH ₂ C 1-4

(CH ₃ J ₃ C- ^Λν CH ₂ CH ₂ CON _n ^ O

Melting point: 123 to 124 ° C

Analysis: Calculated: C 73.14 H 8.18 N 5.69 Found: C 73.21 H 8.18 N 5.73

009837/2273

-33 - '2008A64

(CH ₃ KC, (56)

N. CONHC ₈ H ₁₇

Söhjmelzpuiikt: 34 to 36 C

Analysis: Calculated. V C 75.84 H 9.15 N 5.53

Found: C- 75.87, H 9.40. N ^ 5.38 ..

Melting point: 84 Ms 85 °

Analysis: Calculated: C 77.97, H 10.28 N, 4.33 Found: C 77.93 H 10.29 N 4.39

('GH ₃ ) ₃ Q (58)

"« Yz = s - ₂ -ü S ₅ ^ / sys

CON P

Melting point: 153 to 154 °. C.

Analysis: Calculated VC "72.38 H-7.81 N. 6.03

gelulleW ^ i 0 ^ 71.96 H 7.78- N 6.07 009837/2273

Example 6

A mixture of 100 parts of unstabilized polypropylene (Profax 6501, Hercules Powder) and 0.2 parts of a compound according to the table below is processed into a pellet on the calender at 170 C and then at 230 C and a pressure of 40 kg / cm m pressed into a sheet 1 mm thick. The so obtained. Plates are subjected to accelerated oxygen aging at 140 ° C (air, normal pressure). The time it takes for the first visible cracks to appear is a measure of the antioxidant effect of the added compound.

009837/2273

Tabel

clogged compound

Time to crack formation in hours. 140 ° C

without addition

A. Commercially available antioxidants 2,6-di-tert-butyl-4-methylphenol

Kethylene bis (3-methyl-4-hydroxy-5-tert-butylbenzene) .

Thio-bis- (2-methyl-4-hydroxy-5-tert, butylbenzene)

3. Compounds according to the invention

HC-C-H ₂ C-C

HC

H-C

C (CH,)

28

100

190

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added compound time to crack formation in hours at 140 ° C

YH ₂ - <"

^G 12 ^H 25

E.
C (CH-)

3'3

375

580

009837/2273

■■ • ν. ■■. - Ύϊ -

2ΜΒ4Β4

". Example 7 · ·

Freshly distilled olive oil, which can contain 0.2% of the compounds listed in the table, is oxidized for 20 minutes at 140 ° C in a pure stream of oxygen. Then 1 g of it is dissolved in a mixture of 20 ml of carbon tetrachloride, 20 ml of chloroform and 20 ml of freshly distilled glacial acetic acid. The oxygen dissolved in gaseous form is displaced by means of a strong stream of nitrogen, whereupon 1 ml % saturated potassium iodide solution is added. The mixture is then stirred well for 5 minutes under a sticky substance atmosphere so that quantitative iodine excretion takes place. After adding 100 ml of freshly distilled water and a little starch solution as an indicator, titrate immediately with 0.002 η sodium, thiosulphate solution: until the blue coloration disappears *

Peroxide number. (= Miliequivalents of peroxidic oxygen) / kg =

= ml sodium thiosulfate solution) 2

Tabel · ' · -

Peroxide number

Olive oil ,, no addition :, freshly distilled 0

Olive oil, without addition, 20 Mi®., Oxidized 55 ^ i

Olive oil, with 0.2 %> of the compound of the formula

(27) ·, 20 min, oxidized 226

Olive oil with 0.2 % of the compound of the formula

i 42), 20 min * oxidized. _{/ s} 212

Example 8

100 parts of polyethylene powder (Microthene 722, USI) are mixed dry with 0.2 parts each of one of the compounds of formula (27) or formula (42) and then on a two-roller mill at 110 ° C. for 3 minutes to form a homogeneous skin processed. This is then compressed in a press at I30 ⁰ C for 3 minutes into a 1 mm thick plate. To determine the melting index, the plates are cut into small chips. The melting index is determined according to ASTM D-I238-62 T, method E. The increase in the melting index is a criterion for the antioxidant effect of the compounds mentioned.

Tabel

Melt index (in grams)

Polyethylene, without additive polyethylene with 0.2 # of joint of formula (27)

Polyethylene with 0.2 % of the compound of formula (42)

3, 29 3, 22nd 3,

0098 37/2273

Example 9

A mixture consisting of

100 parts of isoprene rubber, 5 parts of zinc oxide

10 parts of titanium dioxide (Kronos RN- 56, Bayer paint factories)

75 parts of barium sulfate

1 part stearic acid

1.5 parts of 2-mercaptobenzothiazole * \

2 parts of sulfur m 1 part each of the compounds of the formula (27) or

of formula (42)

is on a two-roll mill at 70 ° C for 30 minutes Homogeneously mixed and then vulcanized for 20 minutes in a press at 140 ° C to give sheets 1 mm thick pressed. From this, dumbbell-shaped, 8 cm long test specimens are punched out, which are then placed in a convection oven 100 ° C for 50 hours. By measuring the Breaking load and elongation at break before and after aging, one can see the decrease in mechanical strength or the antioxidant effect recognize the named connections.

009837/2273

Tabel

Tensile strength
DIN-DVM 3504 after Addition, not aged fracture
load
Kp / mm ² fracture
strain
in $> Isoprene rubber , without Additive, aged 50 hours 1.33 1160 Iscpren rubber , without Part of the connection of the 0.1 181 Iscpren rubber , with 1 aged ? orael (27), 50 hours Part of the connection of the 0.79 959 Isoprene rubber with 1 aged formula (42), 50 hours 0.67 983

009837/2273

Claims (4)

Claims where R is a hydrogen atom, an alkyl radical with 1 to 12 carbon atoms, a cyanoalkyl radical with 2 to 4 carbon atoms, an alkoxy radical with 1 to k carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to k carbon atoms in the alkyl part, a trifluoromethyl radical, a halogen atom or a group - (CHp) -CO-E, in which E is a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, an optionally substituted alkylamino radical having 1 to 18 carbon atoms, an optionally substituted hydrazine or a morpholine radical and ρ the numbers 0, 1 or 2, η is an integer from 1 to 3, Χ-, an oxygen atom, a sulfur atom, an -NH- or -NQ-- grouping, Q _{1 is} an alkyl radical of 1 to 18 carbon atoms, Y is a branched one Alkyl radical with 1 to -4 carbon atoms and Z, a hydrogen atom or a branched alkyl radical with 1 to 4 carbon atoms _; , mean. · 009837/2273 2. Compounds according to claim 1, which of the formula C-CH ₉ -CH ₉ -ςς_3-OH (Hi). C (C ^) ₃ correspond ,, where Ri is a hydrogen atom or an alkyl group with 1 to 12 carbon atoms, Rp is a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, a cyanoalkyl group with 2 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a phenyl group, a phenylalkyl group with 1 to 4 carbon atoms in the alkyl part, a halogen atom or a group (CHp) -CO-E ,, where E _{1 is} a hydroxyl group, an alkoxy group with 1 to 18 carbon atoms, an alkylamino group with 1 to 18 carbon atoms or a morpholino group and ρ is an integer 0 , 1 or 2, m is the integer 1 or 2 and Xi an oxygen atom, a sulfur atom or an -NH- group mean. 3 · Compounds according to claim 1, which the formula 1\ Vm "" C-CH ^ -CH 009837/2273 correspond, in which R, a hydrogen atom or an alkyl radical with 1 to 12 carbon atoms, Rx a hydrogen atom, an alkoxy radical with 1 to 4 carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to 4 carbon atoms in the alkyl part, a trifluoromethyl radical or a halogen atom, m the whole Number 1 or 2, X, an oxygen atom, a sulfur atom, an -NH- or NQ, grouping and Q ₁ denotes an alkyl radical having 1 to 18 carbon atoms. 4. Compounds according to claim 1, which of the formula correspond, in which R, a hydrogen atom or an alkyl radical with 1 to 12 carbon atoms, R, a hydrogen atom, a cyanoalkyl radical with 2 to 4 carbon atoms, an alkoxy radical with 1 to 4 carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to 4 carbon atoms in the alkyl part, a trifluoromethyl radical, a halogen atom, or a group - (CH ₂ ) -CO-E, in which E is a hydroxyl co group, an alkoxy group with 1 to 18 carbon atoms, * ■ ** an optionally substituted alkylamino radical with 1 n> to 18 carbon atoms, an optionally substituted hydryzine or a morpholine radical and ρ corresponds to 0, 1 or 2, and m is the integer 1 or 2. 5 · Compounds according to claim 1, which the formula in which R ₂ , a straight or branched alkyl radical with 1 to 12 carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to 4 carbon atoms in the alkyl part, a halogen atom or a group - (CH ₂ ) _D -C0-E, in which E is a hydroxyl group , an alkoxy group with 1 to 18 carbon atoms, an optionally substituted alkylamino group with 1 to 18 carbon atoms, an optionally substituted hydrazine or a morpholine group and ρ 0, 1 or 2 corresponds, and R (- a hydrogen atom or, if R ₂ Alkyl radical means, likewise means an unbranched or branched alkyl radical having 1 to 12 carbon atoms. 6. Compounds according to claim 1, which of the formula ^R ^ ^f ο C-CH ₂ -CH ₂ -C =? ^R 4 ^NN C (CH ₃ ) ₃ 009837/2273 correspond, where R ^ ^{1 is} an unbranched or branched alkyl radical with .1 to 12 carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to 4 carbon atoms' in the alkylsil * a chlorine atom, a hydrogen atom or a group - (CH ₂ ) -CO-E ₁ denotes in which E, a hydroxyl group, an alkoxy group with 1 to 18 carbon atoms, an alkylamino group with 1 to 18 carbon atoms, a morpholino group and p, 0 or 2, and R ₁ J is a hydrogen atom or, if R ₁ / is an alkyl group means, also means an unbranched or branched alkyl radical having 1 to 4 carbon atoms. 7. Compounds according to claim 1, which have the formula C-CH ₀ -CH ₀ // 2 2 ■ correspond to where Rg and R ^. one instantaneous each or branched alkyl radical with 1 to 12 carbon atoms and Rg is preferably in the 6-positions or 7 of the benzene ring. 909837/2273 8. Use of the compounds of the formula • ^s - 4 wherein R is a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, a cyanoalkyl group with 2 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a phenyl group, a phenylalkyl group with 1 to 4 carbon atoms in the alkyl part, a trifluoromethyl group, a halogen atom or a Group - (CHp) -CO-E, in which E is a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, an optionally substituted alkylamino radical having 1 to 18 carbon atoms, an optionally substituted hydrazine or a morpholine radical and ρ the P numbers 0, 1 or 2, η is an integer from 1 to 3, X-, an oxygen atom, a sulfur atom, an -NH- or -NQ, - grouping, Q, an alkyl radical of 1 to 18 carbon atoms, Y, a branched alkyl radical with 1 to 4 carbon atoms and Z, a hydrogen atom or a branched alkyl radical having 1 to 4 carbon atoms, as antioxidants. 009837/2273 9. Use according to claim 8 of the compounds the "formula wherein R ^ ^{1 is} a hydrogen atom or an alkyl radical
an alkyl radical having 1 to 12 carbon atoms, a
Cyanoalkyl radical with 2 to 4 carbon atoms, an alkoxy radical with 1 to 4 carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to H carbon atoms in the alkyl part, a halogen atom or a group (CHp) -CO-E ,, where E,
a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, a Tn alkylamino group having 1 to 18 carbon atoms or a morpholino group and ρ is an integer
0, 1 or 2, m the whole number 1 or 2 and X | an oxygen atom, a sulfur atom or an -NH- group
mean. · 10. Use according to claim 9 of the compounds of the formula C (CH ) 009837/2273 wherein R is a hydrogen atom or an alkyl radical having 1 to 12 carbon atoms, R «is a hydrogen atom, an alkoxy radical with 1 to 4 carbon atoms, a phenyl radical, a phenylalkyl radical with Γ to 4 carbon atoms in Alkyl part, a trifluoromethyl radical or a halogen atom, m the integer 1 or 2, X ₁ an oxygen atom A sulfur atom, an -NH- or NQ _{1 group} and Q _{1 is} an alkyl radical having 1 to 18 carbon atoms. 11. Use according to claim 10 of the compounds the formula C (CH ₅ ). wherein R _{1 is} a hydrogen atom or an alkyl group with 1 to 12 carbon atoms, R is a hydrogen atom, 'a cyanoalkyl group with 2 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a phenyl group, a phenylalkyl group with 1 to 4 carbon atoms in the alkyl part, a Trifluoromethyl radical, a halogen atom, or a group - (CHp) -CO-E, in which E is a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, an optionally substituted alkylamino radical having 1 to 18 carbon atoms, an optionally substituted hydryzine or a morpholine radical and ρ 0, 1 or Corresponds to 2, and m is the integer 1 or 2. 0098 3 7/2273 1MS4S4 12 »Checking the use of legal terms i formulas connect 4> where R ^ is an unbranched or branched alkyl radical with 1 to 12 carbon atoms, a phenyl radical »a rienylaicyl radical with 1" to ^ fe atoms in the alkyl group, a maleic atom or a group - (GHgL-GO-E, in which E & 1Ά & ϊ? Hydrokyl group ^ group with 1 to 18 carbon dioxide breaths, one service case if necessary substituted aikyiaiiinorest with 1 to 18 carbon atoms, an optionally substituted ^ or a fine morphiloline residue and ρ Ö · »1 or 2 e and c a Wasserstöffatöfti or if Tk © ^ neti Aikyirest means, ebewfall% a üftveTz ^ elgten t) the V Älkyirest ttiit 1 to 12 Kohl ^ ö ^ fätomen 13, drift fertilization according to n the formula del? Connecting wherein R2, ^{1 is} a straight or branched alkyl radical with 1 to 12 carbon atoms, a phenyl radical, a phenylalkyl radical with 1 to 4 carbon atoms in the alkyl part, a chlorine atom, a hydrogen atom or a group - (CH ₂ L -CO-E ₁ , in which E , atoms, a hydroxyl group, an alkoxy group having 1 to l8 KohlenstoffatöBien, a Älkylaminorest having 1 to 18 carbon, a morpholino radical and p ^ 0 or 2 corresponds to, and% J EIAA hydrogen atom or, where Tk ¹ represents an alkyl group, also an unbranched or branched alkyl radical having 1 to 4 carbon atoms. 14. Use according to claim. 13 ä & r compounds of the formula C-CH ₀ -CH ₀ // · 2 2 in which Rg and R ₇ each denote an unbranched or branched alkyl radical having 1 to 12 carbon atoms and Rg is preferably in positions 6 or 7 of the benzene ring. 009837/2273