DE2410370A1 - USE OF PYRAZOLE COMPOUNDS TO STABILIZE ORGANIC MATERIALS - Google Patents

Description

Di? L.-lng.P.Wi: th

Di. V. SJ ·· i .'Uv.v-> rzik

DW - ■ · ■. O Or., -. Berg

D-. r. · -.:■. ' :. ..J.Gudel

<S Fron ¹ ; ■ .. ·! ■ '' ■ ·· ''_'r:.r; .. he Str..

ANDOZ Α.Θ.

Case 150-3473

Use of pyrazole compounds for stabilization of organic materials.

The present invention relates to the use of pyrazole compounds of the formula

O Il R ₃ C - R "

^R i ■

to stabilize organic materials,

409838/1075

- 2 -. Case 150-347 3

241037Q

where R is an alkyl radical with 1-22 carbon atoms, a cycloalkyl or cycloalkylalkyl radical with up to 12 carbon atoms and the aliphatic ^ chain of the alkyl radical can be interrupted by sulfur, an aralkyl radical with up to 12 carbon atoms and the aryl nucleus of the Aralkyl radical can additionally be substituted by 1 or 2 hydroxyl groups and / or 1 or 2 alkyl, cycloalkyl, cycloalkylalkyl radicals with 1-12 carbon atoms, a phenyl radical which can be substituted by halogen, cyano, hydroxyl, I or 2 alkyl radicals with 1-12 C atoms, 1 or 2 alkoxy radicals with 1-12 C atoms, phenyl, -SO H and / or the radical R ₄ -O- or R -SO--, can be substituted,
R- one of the meanings of R ,,. Or a

Remainder of the furan, thiophene, benzothiophene, Indole, pyridine or quinoxaline, these radicals being replaced by 1 or 2 halogen atoms, 1

or 2 alkyl or alkoxy radicals with 1-4 carbon atoms can be substituted and carry a maximum of 2 substituents, or one with 1 or 2

Chlorine atoms-substituted alkyl radical with 1-4 C atoms,

Usually a phenyl radical which can be substituted by 1 or 2 alkyl radicals with 1-8C atoms,

R, one of the meanings of R, or cyano or -COOR ₅ ,

R, - an alkyl radical, with .1-12 atoms or one Cycloalkyl or cycloalkylalkyl radical with up to 12 carbon atoms or a phenyl radical, which can be substituted by hydroxyl and / or 1-2 alkyl radicals with 1-8 carbon atoms, and

409838/1075

- 3 -. Case 150-3473

Me hydrogen or an equivalent of a 2

valuable metal ions
mean.

A preferred embodiment is the use of compounds of the formula

(la)

^{0Me <}

wherein R ¹ and R 'independently of one another are ″

JL -3,.

Alkyl radical with 1-8 carbon atoms or a phenyl radical, which is replaced by halogen and / or 1 or 2 alkyl radicals can be substituted with 1-4 carbon atoms,

Me hydrogen, or an equivalent of nickel / zinc, manganese, copper, chromium, calcium, barium, Mean cobalt and R "has the above meaning. A preferred embodiment is the use of Compounds of the formula

0
Hl ^ -CR ^

OMe ¹

wherein R ' _{2 is} an alkyl radical with 6-18 carbon atoms, a cycloalkyl radical with 6-8 carbon atoms, an aralkyl radical with 7-10 carbon atoms whose aryl nucleus is additionally by hydroxyl and / or

409838/1075

- 4 - Case 150-3473

1 or 2 alkyl radicals can be substituted with 1-6 carbon atoms, a phenyl radical which by 1-3 halogen atoms, 1 or 2 hydroxyl groups, 1 or 2 alkyl and / or 1 or 2 Alkoxy radicals with 1-8 carbon atoms and / or phenyl can be substituted, or a radical of the Furans, thiophene or benzothiophene, these heterocyclic radicals being represented by 1 or 2 Halogen atoms or an alkyl radical with 1-4 carbon atoms can be substituted, means

and R'w R'o ^{and Me} ' ^d ^ ^{e have the} above meaning. Another preferred embodiment is the use of compounds of the formula

OMe "Y2 ( _Ic )

in which R "is an alkyl radical having 8-18 carbon atoms, a cycloalkyl radical with 6-8 carbon atoms, an aralkyl radical with 7-10 carbon atoms, its aryl nucleus in addition can be substituted by hydroxyl and / or 1 or 2 alkyl radicals with 1-6 carbon atoms, a phenyl radical, by 1 or 2 halogen atoms, a hydroxyl, 1 or 2 alkyl and / or alkoxy radicals with 1-8 C atoms and / or phenyl can be substituted, but carries a maximum of 3 substituents, or one Remainder of the furan, thiophene or benzothiophene, which, by 1 or 2 halogen atoms or one Alkyl radical with 1-4

409838/1075

- 5 - Case 150-3473

C atoms can be substituted, Me "nickel, zinc, manganese, copper, chromium,

or cobalt mean and

R 'and R' have the above meanings. Mention should also be made of the use of connections the formula

(Id)

OMe "3/2

wherein R "denotes the phenyl radical which is replaced by an alkyl radical

can be substituted with 1, 2, 3 or 4 carbon atoms, or methyl,
R "is an alkyl radical with 1, 2, 3 or 4 carbon atoms

or the phenyl radical,

R "'is an alkyl radical with 8-11 carbon atoms, a cyclohexyl radical, a phenylethyl radical, the aryl nucleus of which is additionally replaced by a hydroxyl group and / or 1 or 2 alkyl radicals with 1, 2, 3 or 4 C atoms can be substituted, a phenyl radical, which can be replaced by a hydroxyl group, 1 or 2 Alkyl or an alkoxy group with 1, 2, 3 or 4 carbon atoms and / or phenyl can be substituted can, but carries a maximum of 3 substituents, or a radical of furan, thiophene, benzothiophene, which can be substituted by a chlorine atom or a methyl or ethyl group,

mean and Me "have the above. meaning.

403838/1075

- 6 - Case 150-3473

The following compounds of the formula (II) or the above compounds of the formulas (Ic) and (Id) are new. The present invention also relates to a process for the preparation of compounds of the formula

ι!

^ N ^^ OMe

wherein R "" is an alkyl radical with 8-18 carbon atoms, a cycloalkyl radical with 6-8 carbon atoms, a Aralkyl radical with 7-10 carbon atoms whose aryl nucleus is additionally through hydroxyl and / or 1 or 2 alkyl radicals can be substituted with 1-6 carbon atoms, a phenyl radical which by 1 or 2 halogen atoms, a hydroxyl, 1 or 2 alkyl and / or alkoxy radicals with 1-8 carbon atoms and / or phenyl can be substituted

can, where this phenyl radical is at most 3 / Me 'wasserstoi'x and this phenyl radical ■. SritertrrKfelliröli-carries ¹ un-d-Wenny- aus-

is finally substituted by halogen has at least 2 halogen atoms, R ⁿ "in the following also a radical of the furan,

Thiphens, Benzothiophens, Inöols, Pyridins or quinoxaline, these radicals being replaced by 1 or 2 halogen atoms, 1 or 2 alkyl or Alkoxy radicals substituted with 1-4C atoms

409838/1075

- 7 - Case 150-3473

can be and carry a maximum of 2 substituents, means and

R, R and Me have the above meaning, which one characterized in that one mole of the compound of the formula

^R 3_.

II, 2 (III)

N C

^R i

with one mole of the compound of formula

R "" COCe (IV)

converts, and if Me is an equivalent of a metal ion means that the product obtained is converted into the corresponding Me-salt. The production method is preferred of compounds of the formula

0 i-R ".

^N -L OMe ¹¹ ^ ₂ (Ic)

wherein R ^{1 R} _"2 ^'R * 3 ^{and Me' o} g ^{e bi} meaning, which is characterized in that 1 mole of the compound

409838/1 075

- 8 - Case 150-3473

N C = O

^ _n / (Ilia)

ii
^R 1

with one mole of the compound of formula

R " ₂ COCe (IVa)

converts, and then converts the product obtained into the Me "salt. The process is preferred also for the preparation of compounds of the formula (Id), which is characterized in that 1 mol the connection

^ K - ° aim

reacted with 1 mol of the compound of the formula R ¹¹ LCOCl (IVb), and the product obtained is converted into the Me "salt.

Unless otherwise specified, come as alkyl radicals is, naturally occurring or synthesizable primary, secondary or tertiary, straight-chain or branched question:

Examples of such primary radicals are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, ündecyl, dodecyl, hexadecyl, heptadecyl, octadecyl, docosanyl.

Examples of secondary radicals are isopropyl, 2-butyl,

409838/1075

- 9 - Case 150-3473

3-methyl-2-butyl, 2-pentyl, 2-hexyl, 3-hexyl, 2-methyl-3-pentyl, 3-octyl, 4-octyl, 2-decyl, 5-decyl, 2,2-dimethyl-3-octyl, 2-heptadecyl, 2-hexadecyl, 2-nonadecyl. Examples of tertiary radicals have the following meanings: tertiary butyl, 3-methyl-3-hexyl, 1-methyl-cyclohexyl, tert. Octyl.

Examples of cycloalkyl radicals are: cyclopentyl, cyclohexyl, cycloheptyl, 2-, 3- or 4-methyl-cyclohexyl, Cyclooctyl, cyclododecyl.

Examples of cycloalkylalkyl are: Cyclohexyl-methyl, 2-cyclohexyl-ethyl, cycloheptyl-methyl. Examples of branched alkyl radicals are: 2-methyl-1-propyl, 2,2-dimethyl-1-propyl, 2-methyl-1-butyl, 2,2-dimethyl-1-decyl.

Examples of aralkyl radicals are: benzyl, 2-phenylethyl. Examples of radicals whose aliphatic chain is interrupted with sulfur are 2-methylthioethyl, 2-dodecylthioäthy1, Methylthiomethy1.
Examples of substituted phenyl radicals are

Further examples for R are:

409838/1075

Case 150-3473

U-

The nickel complexes can also contain 1-2 moles of water of crystallization.

The reaction is advantageously carried out in an inert organic solvent, it being possible for the starting materials to be dissolved or also suspended therein. The mixture is preferably heated to from 20 ^° C. to 110 ^° C., with hydrogen chloride being split off. This can be allowed to escape from the reaction vessel at an elevated temperature. In general, however, it is more convenient to carry out the reaction in the presence of acid-binding agents, v / ie, for example CaO, alkali metal carbonate or bicarbonate, pyridine, trialkylamine or dialkylaniline. The reaction takes place in the absence of moisture. Suitable solvents are, for example, benzene, xylene, cymene, diphenyl ether, tetrahydrofuran and dioxane. If Me is a divalent metal ion, the compound of the formula (I) in which Me is hydrogen can first be converted into the alkali metal salt, for example by dissolving the compound of the formula (I) in alcohol and an alkali hydroxide such as NaOH or KOH inflicts. A salt, for example the chloride, is then added to the reaction mixture, whereupon the desired product is obtained.

409838/1075

- 11 - Case 150-3473

A preferred embodiment is direct production of the metal salt from the compound of the formula (I) in which Me is hydrogen, by adding the latter directly with a Me acetate such as the acetate of nickel, zinc, manganese, cobalt, copper, Calcium or barium to react. This reaction is preferably carried out in an alcohol such as methanol, ethanol, propanol, etc. at room temperature up to Reflux temperature of the solvent. At the The product mostly precipitates when it cools down.

If this is not the case to a sufficient extent, then it can

the precipitation can be accelerated by adding water.

For use as stabilizers, the compounds incorporated into light-sensitive substances or as a protective layer on the -'- to be protected Substances applied. The new compounds used in this way retain their stabilizing effect the sensitive substances from destruction. Organic materials suitable for this treatment are for example: polyolefins, especially polyethylene and polypropylene, polyester, polymethy! methacrylate, Polyphenylene oxides, polyurethanes, polystyrene, ABS terpolymers, polyamides such as nylon, polypropylene oxide, Polyacrylonitrile and corresponding copolymers. The compounds according to the invention are preferably used to stabilize polypropylene, polyethylene, polyester, polyamide, polyurethanes, polyacrylonitrile, ABS terpolymers, terpolymers of acrylic ester, Styrene and acrylonitrile, copolymers of styrene and acrylonitrile or styrene and butadiene.

Natural substances can also be stabilized, such as

403838/1075

- 12 - Case 150-3473

for example rubber, cellulose, wool and silk. The substances to be protected may be in the form of plates, bars, coatings, sheets, films, tapes _r fibers, granules, powders un in other processing forms or as solutions, emulsions or dispersions exist. The incorporation or coating of the materials to be protected takes place according to methods known per se. A particularly important application method consists in the intimate mixing of a plastic, for example polypropylene in granulate form, with the new compounds, for example in a kneader, and in the

subsequent extrusion. In this way you get a very homogeneous mixture, what a good one Protection is important. When extruding, for example, films, tubes or threads are obtained. Latter can be woven into textiles. In this mode of operation, the stabilizer is closed before processing a textile material mixed with the polypropylene. However, you can also treat textile thread and textile fabric with the new stabilizers, for example in an aqueous liquor which contains a dispersed compound of the formula (I). For this procedure Textiles made of polyethylene terephthalate and cellulose acetate are suitable. Plastics don't necessarily have to be be completely polymerized or condensed before mixing with the new compounds takes place. Man can also be monomers or prepolymers or precondensates mix with the new stabilizers and only afterwards convert the plastic into its final shape Condensing or polymerizing.

The new stabilizers can not only be used to clear films, plastics and the like stabilize, they can also be used in opaque,

409838/1075

- 13 - Case 150-3473

semi-opaque or translucent materials, the surface of which is sensitive to degradation by ultra-violet light, air and heat. Examples of such materials are: foamed plastic B, opaque films and coatings, opaque papers, clear and opaque colored plastics, fluorescent pigments, polishes for automobiles and furniture, creams and lotions, and the like.

The amount of incorporated protective agents varies between 0.01-5%, preferably between 0.05-1% based on the weight of the materials to be protected. In the following examples, parts mean parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. The specified structures are secured by microanalysis and spectral analysis.

409838/1075

- 14 - Case 150-3473

example 1

A mixture of 17.4 parts of 1-phenyl-3-methyl-pyrazolone (5), 11.2 parts of CaO and 19.6 parts of 4-tert-butyl-benzoyl chloride is refluxed in 100 parts of dioxane for 30 minutes . The resulting thick paste is poured into 200 parts of water at room temperature with stirring. The resulting brown solution is acidified with dilute HCl, the precipitate which has separated out is filtered off with suction, washed neutral, dried and crystallized from methanol. The connection is obtained from the Srnp. 107-109 ⁰ C of the formula

To produce the nickel salt, 10 parts of the compound obtained are dissolved in 20 parts of methanol and mixed with the stoichiometric amount of nickel acetate. The mixture is then ^{heated to 70 °} C. for 30 minutes and allowed to cool. The precipitated green precipitate is filtered off, washed with methanol / water 1: 1 and dried at 110 ⁰ C. Melting point 205 ^° C. A practically quantitative yield is obtained. The salts of zinc, manganese, cobalt, copper, calcium or barium are obtained in an analogous manner.

409838/1075

- 15 - Cöse 150-3'7

Example 2

A mixture of 8.26 parts of 1,3-diphenylpyrazolone (5), 3.92 parts of CaO and 9.38 parts of 3,5-di-tert-butyl-4-hydroxy-benzoyl chloride are refluxed for 2 hours in 100 parts of dioxane. The mixture is on top cooled to room temperature and poured into a solution consisting of 50 parts of 2N HCl and 100 parts of ice water, poured. The deposited precipitate is filtered off with suction, washed neutral and crystallized from methanol. The compound with a melting point of 187-188 ° C of the formula is obtained

Example 3

3.75 parts of 1,3-diphenyl-4 [3 ', 5'-di-tert. ~ Butyl-4 · - hydroxy] benzoyl-5-hydroxy-pyrazole are in 60 parts Submitted ethanol and heated to 45 °. 4 parts are added to the mixture at the same temperature 2n KOH solution and then 10 minutes with a solution of 0.94 parts of NiCl -6HO in 20 parts of ethanol. The solution immediately turns green and KCl precipitates. After a reaction time of 30 minutes, the KCl is filtered off and the green solution evaporated. The solid residue is washed with Viasser, suctioned off and dried at 120 °. You get the connection from

40983S / 1075

M.p. 250 ^° C. of the formula

Caae 150-3473

C (CII)

The nickel salt can also be produced analogously to Example 1 -

example

34.8 parts of 1-phenyl-3-methylpyrazolone (5) and 13.2 parts of CaO are placed in 40.0 parts of dioxane at room temperature. The mixture is then heated in an oil bath (80 ⁰ C). With stirring, 43.7 parts of Laurinsäurechlorxd starting zuzutropfen at 75 ⁰ C reaction temperature. The acid chloride is added within 45 minutes. The temperature rises to 95 ⁰ C, and in the end result is a thick, brown, readily stirrable paste. After addition of the acid chloride the mixture is allowed / pus to react for 1 hour at 80 ⁰ C v. It is then cooled to 50 ^° C. 100 ml of methanol and 23.0 parts of hydrochloric acid are added in succession. After adding the latter, the mixture is stirred for a further 30 minutes; then added to the mixture all at once with 24.8 parts of nickel acetate and stirred for 30 minutes at reflux (internal temperature: 70 ⁰ C). The precipitated nickel complex is ^{filtered off with suction at 50 °} C., washed halogen-free with 1.5 parts of water and

409838/1075

- 17 - Case 150-34 / 3

then washed 2 times with 30 parts of methanol each time and ^{dried at 110 °} C. Mp. 144-148 ° C. You get
the nickel salt of the compound of the formula

II

N.

^C 6 ^H 5

For the production of the corresponding zinc, cobalt,
Manganese, copper, calcium or Barxum complexes are proceeded analogously as described in Example 1 or 3.

example

A mixture of 53.3 g of 1-phenyl-3-methyl-pyrazolone (5), 18.5 g of CaO and 44.0 g of thiophene-2-carboxylic acid chloride
is stirred in 120 ml of dioxane at 95 ^° C. for 2 hours. After cooling to 50 ^° C., the mixture is added in succession
with 100 ml of methanol and 30 ml of conc. HCl. It is then allowed to stir for a further 30 minutes. The whole is then poured into 500 ml of ice water, a voluminous precipitate separating out. The precipitate is filtered off with suction, washed with water and crystallized from methanol. M.p .: 133-136 ⁰ C. to yield the compound of formula

409Ö38 / 1075

Case 150-3 473

Example 6

A mixture consisting of 20.2 g of 1-phenyl-3-n-propylpyrazolone (5) and 6.2 g of CaO is heated to 75 ° C. in 80 ml of dioxane. At the same temperature the mixture with stirring over 15 minutes with 14.7 g of thiophene-2-carboxylic acid chloride is added, with the reaction temperature rising to 95 ⁰ C. It makes the whole 1 hour at 95 ⁰ C to react further and then distilled dioxane from. The remaining, thick, brown paste is concentrated with 100 ml of methanol and 10 ml. HCl was added and the mixture was refluxed for 30 minutes. The resulting clear brown solution is poured onto 200 ml of ice water. The reaction product precipitates out in the process. The precipitate is filtered off with suction, washed with water and crystallized from ethanol.
M.p. 124-128 ° C. The compound of the formula is obtained

409838/1075

- 19 - Case 150-2473

Example 7

12.5 g of the compound of Example 6, v / ground in 100 ml of methanol at 45 ⁰ C with 5.0 g of nickel acetate 6H ₂ O. The mixture is stirred for 1 hour without further heating. The precipitated green precipitate is filtered off, washed with water and dried at 90 ⁰ C. M.p .: 145-155 ° C. The compound of the formula is obtained

Example 8

18.8 g of 1-p-tolyl-3-methyl-pyrazolone (5) and 6.18 g of CaO are added in 100 ml of dioxane with stirring at 90 ^° C. with 14.7 g of thiophene-2-carboxylic acid chloride within 30 minutes. The dioxane is then distilled off in a water jet vacuum. The thick paste that ^{remains is concentrated at CO 0} C with 80 ml of methanol and 10 ml. HCl was added and the mixture was refluxed for 30 minutes. 11.8 g of nickel acetate-6H0 are then added to the whole, the mixture is stirred for a further 30 minutes and then cooled to room temperature. The resulting green precipitate is filtered off with suction, washed with water and dried. M.p .: 180-184 ⁰ C. to yield the compound of formula

409838/1075

Case

Example 9

A solution of 1.6 g of NaOH in 10 ml of water is added to 11.4 g of the compound from Example 5 in 100 ml of methanol at 45 ^{° C. and the mixture is stirred for 30 minutes.} Then the yellow solution is mixed with 4.6 g of NiCl “.6HO dissolved in 20 ml of water. After the addition of the nickel chloride, a green precipitate separates out, which is filtered off with suction at room temperature, washed with water and dried. M.p .: 175-180 ⁰ C. to yield the compound of formula

409838/1075

- 21 - Cace 150-3473

Example 10

11/4 g of the compound from Example 5 are mixed with 5.0 g of cobalt (II) acetate ^{in 150 ml of methanol at 45 ° C. while stirring.} After the addition of the salt, a precipitate separates out. The yellowish precipitate is filtered off with suction at room temperature, washed with water and dried. M.p .: 165-170 ⁰ C. to yield the compound of formula

The compounds listed in Tables 1, 2, 3 and 4 are prepared in an analogous manner.

409838/1075

Case 150-2473

Table 1

R.

CO-R ₂

R-

CH.

-OH.

CH

CH

CH

OH

C (CH ₃ ).

CH-

C (CH,).

CH ₇

(n)

CH.

409838/1075

Case I5C-3473

Table 1 continued

R.

CH. CH. _T

CH.

CIL

CH.

CH.

- η

408838/1075

Cc-se 150-3473

Table 2

/ Π.

_ Me 2

No.

18th

R.

CH.

Me

Approx

19th

CH.

Ni

20th

CH.

Mn

21

CH.

Cu

22nd

CH.

Approx

23 24

CH.

CH.

- (O) -C (CH)

3'3

Ni Cu

25th

CH.

C (CH ₃ )

Ni

409838/1075

Case 150-3473

Table 2 continued

No.

R.

26th

CH.

O) - OH

27

CH. C (CH ₃ )

HO- (O)

C (CH)

28

CH, (η)

29

CH. C (CH ")

30th

CH.

O) - ^0H

31

CH.

OH
C (CH ₃ > ₃

32

CH. - <oV ~ (o)

33

CH. (OHO)

409838/1075

Case 150- 3473

Table 2 continued

No.

R.

CH, CH.

CH. CH.

CH. (θ) -OCH.

CH. OCH

C (CH ₃ )

C (CH ₃ J ₃

38 ^nC ll ^H 23

39 ^nC ll ^H 23

40

HC ₃ H ₇ - ^nC II ^H 2 3

41

42

HC ₃ H ₇ -

43

44 (")

409838/1075

Case 150-3473

Table 2 continued

No.

R.

do. do

do. do.

do.

do.

C (CH ₃ )

- OH
C.

51

do, do.

do.

53

do HO-Zq) -CH -CH ■
3

CH. H)-

55

do. do.

56

do. do.

409838/1075

Caso I5C-2473

241037Q

Table 2 continued

No. 57

CH.

58 do.

59

do. do.

60

do. do

61 62 63 64 65 66 67

CH.

do.

do.

do.

do.

do,

do. ^C 13 ^H 27

^C 13 ^H 27

^C 15 ^H 31

^C 15 ^H 31

^C 17 ^H 35

^C 17 ^H 35

409838/1075

Cc «E3 150-3473

Table 3

R_ CO-R-
InC
--N- ^ OH
K No. ^R l ^R 3 O- ÖÖ & - H ₃ CC ₈ JL I.
69 do. do. ^cl isi0 70 do. do. 71 do. CH ₃ - do. 72 H3O- © - CH ₃ - do. 73 11-C ₃ H ₇

Ό 9838/1075

Case 150-3473

Table 4

R.

O
CU-R ₂

O - Me

1/2

No.

R.

Me

74

CH.

Zn

oil

do.

do.

Mn

do.

do.

do.

Approx

do.

do.

do.

Cu

do.

do.

Mn

do

do.

do.

Zn

do.

do.

do.

Cr

do

81

CH.

Cr

do.

do.

do.

Mn

do.

do.

do.

Zn

do.

84

Ni

409838/1075

No.

Continuation of table 4

Case 150-3473 2410370

85

86

CH.

CH.

do.

87

CH.

do.

do.

88

do.

H ₃ C

XsX

89

do.

do.

do.

90

do.

do.

do.

91

do.

do.

Cl

92

93

do.

do.

do.

Mn

do.

do.

94

do.

do

Ni

do.

95

do.

do

CH.

Mn Ni

do.

N. "Cl Cl

9 ₇

do.

do.

Zn

do.

40 98 38/1075

Case 3!> 0 ~ 3473

Continuation of table 4

No. ^R l ^K 3 Me ^R 2 98 H ₃ C - @ - CH ₃ Ni 99 do. • do Zn do. 100 do. do. Mn do.

In addition, the following connections are also to be made

to name:

No. 10t

N.

CH.

^H 3 ^C.

0
Il
C. wherein Me = Ni (No. 103 a) Il Me = Zn (No. 103 b) Me II Me = Co (No. 103 O '1/2

CH.

409838/1075

- 33 - Case 3 50-3473

Usage example

Unstabilized polypropylene is on a roller mill at 180 ° with 0.5% of the compound Numbers 25, 28, 43, 52 of Table 2 and the compound from Example 9 are intimately mixed and formed into films processed with a thickness of 0.3 mm. These are tested for durability in a climate test using the De La Rue method checked. The test is carried out at 40 °, at 75% relative humidity, with strong air renewal, with 16 Sunlamps and 16 blacklamps from Philips. In in an analogous manner, non-stabilized polyvinyl chloride containing 0.5% of compound no. 17 from Table 2 was obtained tested in the climate test.

Similar results are obtained for polyethylene, ABS terpolymers, Polyethylene terephthalate, cellulose acetobutyrate, polyamide 6, polystyrene, polycarbonate and polyurethane.

409838/1075

Claims (1)

- 34 - Case 153-3473 Pat ent a η sayings
1. Use of pyrazole compounds of the formula O
ιί
R ₀ C- R " (D ^N "" OMe ^R i for stabilizing organic materials, where R is an alkyl radical with 1-22 carbon atoms, a cycloalkyl or cycloalkylalkyl radical with up to 12 carbon atoms and the aliphatic chain of the alkyl radical can be interrupted by sulfur, an aralkyl radical with up to 12 carbon atoms Atoms and the aryl nucleus of the aralkyl radical can additionally be substituted by 1 or 2 hydroxyl groups and / or 1 or 2 alkyl, cycloalkyl, cycloalkylalkyl radicals with 1-12 C atoms, a phenyl radical which can be substituted by halogen, cyano, hydroxyl, I or 2 Alkyl radicals with 1-12 carbon atoms, 1 or 2 alkoxy radicals with 1-12 carbon atoms, phenyl, -SO H and / or the radical R ₄ -O- or R-SO ₃ -, can be substituted,
R one of the meanings of R ,, or a Remainder of the furan, thiophene, benzothiophene, indole, pyridine or quinoxaline, where these radicals by 1 or 2 halogen atoms, 1 or 2 alkyl or alkoxy radicals can be substituted with 1-4 carbon atoms and at most 2 sub- 409838/1075 - 35 - Case 150-3473 carry substituents, or an alkyl radical substituted with 1 or 2 chlorine atoms with 1-4 -C atoms, R. a phenyl radical, which can be substituted by 1 or 2 alkyl radicals with 1-8 carbon atoms, R one of the meanings of R or cyano or -COOR ₅ , R ₁ - an alkyl radical with 1-12 carbon atoms or a cycloalkyl or cycloalkylalkyl radical with up to 12 carbon atoms or a phenyl radical which can be substituted by hydroxy and / or 1-2 alkyl radicals with 1-8 carbon atoms , and Me are hydrogen or an equivalent of a divalent metal ion. 2. Use according to claim 1 of compounds of the formula OMc ¹ Wherein R 'and R' independently of one another an alkyl radical with 1-8 carbon atoms or a phenyl radical, the can be substituted by halogen and / or 1 or 2 alkyl radicals with 1-4 carbon atoms, Me 'hydrogen, or an equivalent of nickel, zinc, manganese, copper, chromium, calcium, barium, Cobalt mean and R "the meaning according to the patent claim Has.
3. Use according to claim 1 of compounds of the formula 409838/1075 - 36 - Case 150-3473 wherein R 'is an alkyl radical with 6-18 carbon atoms, a cycloalkyl radical with 6-8 carbon atoms, a Aralkyl radical with 7-10 carbon atoms whose aryl nucleus is additionally through hydroxyl and / or 1 or 2 alkyl radicals can be substituted with 1-6 carbon atoms, a phenyl radical which by 1-3 halogen atoms, 1 or 2 hydroxyl groups, 1 or 2 alkyl and / or 1 or 2 Alkoxy radicals with 1-8 carbon atoms and / or phenyl can be substituted, or a radical of the Furans, thiophene or benzothiophene, these heterocyclic radicals being represented by 1 or 2 Halogen atoms or an alkyl radical with 1-4 carbon atoms can be substituted, means and R '-. / R'ο and Me' have the above meanings. 4. Use of compounds according to claim 1 of the formula 409838/1075 Case i3Q-3473 wherein R "is an alkyl radical with 8-1B carbon atoms, a cycloalkyl radical with 6--8 carbon atoms, an aralkyl radical with 7-10 carbon atoms, its aryl nucleus additionally be substituted by hydroxyl and / or 1 or 2 alkyl radicals with 1-6 carbon atoms can, a phenyl radical, which is replaced by 1 or 2 halogen atoms, a hydroxyl, 1 or 2 alkyl and / or alkoxy radicals with 1-8 carbon atoms and / or phenyl can be substituted, however carries a maximum of 3 substituents, oclci * one Remainder of the furan, thiophene or benzothiophenes, which by 1 or 2 halogen atoms or one Alkyl radical with 1-4 carbon atoms can be substituted, Me "mean nickel, zinc, manganese, copper, chromium, or cobalt and R 'and R' have the meaning according to claim 2. 5. Use according to claim 1 of compounds of the formula R ". 0 C-R IN THE N. OMe "5/2 (Id) where R " the phenyl radical, which is replaced by an alkyl radical can be substituted with 1, 2, 3 or 4 carbon atoms, or methyl, 409838/1075 - 38 - Case 15C - 3473 R "is an alkyl radical with 1, 2, 3 or 4 carbon atoms or the phenyl radical, IV'l an alkyl radical having 8-11 C atoms, a cyclo hexyl radical, a phenethyl radical, the aryl nucleus may additionally be substituted by a hydroxyl group and / or 1 or 2 alkyl groups having 1,2,3 or C-atoms, a phenyl radical , - which may be substituted by a hydroxyl group, 1 or alkyl or an alkoxy group having 1,2,3 or 4 carbon atoms and / or phenyl, but transmits more than 3 substituents, or a radical of the furan, thiophene, benzothiophenes, which can be substituted by a chlorine atom or a methyl or ethyl group,
mean and Me "have the meaning according to claim 4. 6 / The compounds of the formula 0
^R 3. - ^C " ^RI " ² (ID ^ N OMe wherein R "" is an alkyl radical with 8-18 carbon atoms, a cycloalkyl radical with 6-8 carbon atoms, an aralkyl radical with 7-10 carbon atoms, whose aryl nucleus is additionally replaced by hydroxyl and / or 1 or 2 alkyl radicals with 1-6 C atoms may be substituted can, a phenyl radical, which is replaced by 1 or 2 halogen atoms, a hydroxyl, 1 or 2 alkyl 409838/1075 -'39 - Case 150-3473 and / or alkoxy radicals can be substituted by 1-8 carbon atoms and / or phenyl, this phenyl radical having at most 3 substituents, and if Me is hydrogen and this phenyl radical is exclusively substituted by halogen, it has at least 2 halogen atoms / R "" iir . further also a remainder of furan, thiophene , benzothiophene , indol, pyroline. or quinoxaline, where these radicals can be substituted by 1 or 2 haloene atoms, 1 or 2 alkyl or alkoxy radicals having 1-4 carbon atoms and have a maximum of 2 substituents and R , R and Me have the meaning according to claim 1. 7. The compounds of the formula (Ic) according to claim 4. 8. The compounds of the formula (Id) according to claim 5. 9. Process for the preparation of the compound of formula (II) according to claim 6, characterized in that 1 mol of the compound of the formula ³ T ~ - ^CI / 2 (HD NC _n ^R l with one mole of the compound of formula R " ¹¹ COCl (IV) 409838/1075 241G370 - 40 - Case 150-3473 converts, and if Me is an equivalent of a metal ion, the product obtained into the corresponding Me-SaIz converts. 10. A process for the preparation of the compound of the formula (Ic) according to claim 4, characterized in that that you get 1 mole of the compound υιι ₂ MC = O
\ _H / (Ilia) with one mole of the compound of formula R ^ COCl (IVa) converts, and then converts the product obtained into the Me "salt. 11. A process for the preparation of the compound of the formula (Id) according to claim 5, characterized in that that one mole of the compound of formula R " ^ H ^ "* ° (HIb) with 1 mol of the compound of the formula R "'COCl (IVb), and converting the product obtained to the Me "salt. 409838/1075 Oasis 150-3473 12. The method according to claims 9-11, wherein Me or Me ¹ or Me "denotes a metal ion, characterized in that the product obtained is first converted into an alkali metal salt and then with a Me salt or Me'- or Me "~ Salt converts. 13. The method according to claims 9-11, wherein Me or Me ¹ or Me "denotes a metal ion, characterized in that the product obtained is reacted directly with the Me acetate or Me'- or Me" acetate. 14. The compound of formula i
C ₆ H ₅ 15. The compound of formula I ^C 6 ^H 5 16. The compound of formula AT OMn HC (CH ₃ ) ₃ 1/2 C (CH ₃ ) C (CH) 409 8 38/1075 2A10370 Case 150-2473 17. The compound of formula ^H 5 ^C 6 COC-H _n ^{6 5} T " ^0Mn 1/2 ^C 6 ^H 5 18. The compound of formula (CH OMn 1/2 ^C 6 ^H 5 19. The compound of formula ^H 3 ^C. ^ CO- (O) -OCH ₃ "N ^C 6 ^H 5 20. The compound of formula C (CH ₃ ) N. I ^OCO V2 409838/1075 241Q370 Case 150-3473 21. The compound of formula H ₀ C CO ³ X / OMn CH, 1/2 22. The compound of formula H ₃ C. N ONi 1/2 IQJ CH. 23. The compound of formula CO-C ₈ H ₁₇ (n) ONi 1/2 ^C 6 ^H 5 24. · The compound of formula H ₃ C 3/2 ^C 6 ^H 5 (n) 409838/1075 IL.0-3473 Compound of the formula H ₃ C COC ₁₇ H ₃₅ ^C 6 ^H 5 26. Use of the compounds according to claims 1-6 and 14-2 5 for stabilizing polyolefins, polyesters, Polyrae thy Imethacry later ,, polyphenylene oxides, polyurethanes, polystyrene, polypropylene oxide _; Polyamides, polyacrylonitrile, ABS terpolymers, terpolymers of acrylic, styrene and acrylonitrile, copolymers of styrene and acrylonitrile or styrene and butadiene. 27- Use of the compounds according to the claims 1-6 and 14-25 for stabilizing polypropylene, polyethylene. 28- Organic materials that contain one or more compounds according to claims 1-6 and 14-2 5. 29- polypropylene according to claim 27. 3700 / SI / VT 409838/1075