DE2102984A1 - Thiornethylenphenolverbindungen, their production and their use as antioxidants- - Google Patents

Description

American Cyanamid Company, Wayne "New Jersey, V.St.A.

Thiomethylene phenol compounds ^ their production and their use as antioxidants

(Addition to P 19 07 565.D

The invention relates to thiomethylene phenol compounds, Process for their preparation and their use as antioxidants for oxygen-sensitive compounds and aims to improve and / or further develop the subject matter of patent P 19 07 565.1.

The main patent relates to compounds of the formula

109S31 / 2251

wherein the radicals R, which can be the same or different from one another, are lower alkyl radicals, Usually a higher alkyl radical or higher alkylbenzyl radical and Rp is a hydrogen atom or the group

mean.

It has now been found that compounds of the formula

OH

CH ₂ CH ₂ O

(0O) _x -

, "tr

where R is a branched alkyl radical having 3 to 12 carbon atoms, Y is a divalent or trivalent one Hydrocarbon radical with 2 to about 20 carbon atoms, the radical of an organic polycarboxylic acid having 2 to about 14 carbon atoms or the group

η is an integer from 2 to 4, χ 0 or 1 and ζ 0 or 1, where z, when χ 0, also denotes

109831/2251

O 1st to have the same beneficial properties as distinguish the compounds described in the main patent.

The preferred compounds according to the invention include those in which η is 2 and Y is a straight-chain or branched alkylene or thioalkylene group having 2 to about 12 carbon atoms or a mononuclear group aromatic radical of the formula

denotes in which R ₁ , Rp, R, and R ₁ , hydrogen atoms or lower alkyl radicals, which preferably have about 1 to 3 carbon atoms, and m is O or 1.

These connections can be made by various methods, largely depending on availability depends on the starting materials. In general, they are made by reacting an active halomethyl group, e.g. a chloromethyl or bromomethyl group, with a "thiol group, the reaction being carried out in the presence an acid acceptor is carried out.

So these compounds from the corresponding alkylphenols with a chloromethyl substituent in Meta position to the hydroxyl group. This can be in the 3-position of a 2,4-dimethyl-6-alky! Phenol or phenol acetate by reaction with

109831/2251

Hydrochloric acid and formaldehyde or with methylal in the presence of hydrochloric acid and H ₂ SO ₂ , according to the method of R. Wegler and E. Regel, given in Makromol. Chem. 9,1 (1952). The 3-chloromethyl-2, ^1- ldimethyl-6-sec- or -tert. -Alkylphenol prepared by this method can with a hydrocarbon with 2 to 20 carbon atoms, the 2 mercaptomethylene groups, for example an alkyldithlol with 2 to 12 carbon atoms, a xylene dimercaptan such as alpha, alpha'-dimercapto-p-xylene, 1,3-dimercaptomethyldurol and the like, or containing three mercaptomethylene groups as in mesitylenetrimercaptan, can be converted with the aid of a condensation reaction, as illustrated, for example, by the following reaction equation:

III

CH ₂ Eq

CH

+ HS'CH ₂ -Y'-CH ₂ 'SH

CH ₂ * S * CH ₂ 'Y'

+ 2HGl

R is a branched alkyl radical with 3 to 12 carbon atoms and Y ^{1 is} a hydrocarbon radical with 2 to about 20 carbon atoms.

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If desired, however, the 3-chloromethylphenol can be converted into the corresponding 3-mercaptomethyl-2,4-dimethyl-6-sec- or tert-alkylphenol. This can be done by dissolving the chloromethyl compound in tetrahydrofuran, adding at least one molar equivalent of triethylamine, trimethylamine or another acid acceptor and introducing hydrogen sulfide until the formation of mercaptan has ended. Compounds according to the invention can be prepared by reacting 2 or 3 molar equivalents of the 3-mercaptomethyl compounds thus produced with 1 mol of an aliphatic or alkaryl compound which contains two or three active halomethyl A

contains groups, according to the method that is explained in some exemplary embodiments, are produced.
J

Exemplary compounds having active halomethyl groups that can be used therefor are alpha, omega-dichloroalkanes and -dibromoalkanes with 2 to 12 carbon atoms and the trichloro- and tribromoalkanes of the formula

X-CH ₂ R-CH ₂ X,

i

CH ₂ X

where X is chlorine or bromine and R is an aliphatic radical having 1 to 9 carbon atoms. The corresponding chlorine- or bromine-substituted polymethylbenzenes, such as alpha, alpha-dichloro-p-xylene, 1,4-dichloromethyldurol and 2,4,6-tribromomethylmesitylene

109331/2251

used when thiomethylene phenol antioxidants that bridge a mononuclear contain aromatic hydrocarbons.

The reaction between these reagents is carried out in the presence of acid acceptors, e.g. alkali metal carbonates or alkoxides, and preferably in a solvent or a solvent mixture, e.g. tert-butanol, Dimethylformamide or methyl isobutyl ketone. The reaction temperatures are not critical and can range from room temperature to the boiling point of the mixture when reflux conditions are used. the desired reaction products can be purified by recrystallization and, if desired, by chromatography can be further purified on aluminum oxide.

When Y is the residue of an organic polycarboxylic acid having from 2 to about 14 carbon atoms, the starting phenol is following formula

CH ₃

CH ₂ S (-CH ₂ CH ₂ O-) _Z H

wherein R and ζ are as defined above. This compound is combined with an organic polycarboxylic acid halide in Presence of an acid acceptor capable of binding the released hydrogen chloride and in a non-aqueous solvent, e.g. chloroform, tetrahydrofuran or the like, implemented. If ζ 1 means, the starting phenol can by reacting the corresponding

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3-chloromethylphenol obtained with 2-mercaptoethanol will. If Y is the group

N N

represents, the compounds in question can by reacting a 3-halomethyl-2,4-dimethyl-6-tert-alkylphenol with 1 mole of 2,5-dimercapto-l, 3, ⁱ J-thiadiazole in the presence of an acid acceptor for the free \

put hydrogen halide to be produced. The reaction is preferably in an anhydrous solvent, e.g. methyl ethyl ketone, methyl isobutyl ketone or Tetrahydrofuran, and made at reflux temperature. The implementation will continue until the formation of the product is practically complete, whereupon the crystalline reaction product is washed with water and is dried. It can be further purified by recrystallization from benzene and chloroform.

The use of the compounds according to the invention as antioxidants for polyolefins is detailed in the main patent explains what is referred to herein. The invention is further illustrated by the following examples explained.

example 1

3.3 ^l / ethylene bis (thiomethylene) _ / - bis (6-t-butyl-2, iJ-dimethy! Phenol)

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η, α

GH ₂ S-CH ₂ GH ₂ -SCH ₂

A mixture of 33.97 g (0.15 mol) of 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl chloride, 7.05 g (0.075 mol) 1,2-ethanedithiol and 60.72 g (0.60 mol) triethylamine in 225 ml of tetrahydrofuran is heated to 60 to 62 degrees for 19 hours. The triethylamine hydrochloride is filtered off. The filtrate is concentrated to 150 ml and diluted with 250 ml of benzene. The benzene solution is diluted with Washed hydrochloric acid and water and dried over anhydrous sodium sulfate. The salt is removed and the piltrate becomes 11.85 g of a mass of brownish crystals, melting point 125 to 128 degrees constricted.

After recrystallization from a mixture of benzene and hexane (1: 1), 8.6 g of cream-colored crystals are from Melting point 131 to 133 degrees obtained. By chromatographing this product on alumina using a mixture of benzene and chloroform (1: 2) as eluent, an analytically pure sample is obtained. The colorless crystals melt at 1 ^ 3 to Degree.

Calculated: C 70.89; H 8.86; S 13.50; Found: C, 71.09; H 9.02; S 13.21

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Example 2

3,3 '- / tetramethylene-bis (thiomethylene) _ / - bis- (6-t-butyl-2,4-dimethylphenol).

The procedure of Example 1 is 9 »15 g 1,4-Butanedithiol instead of A'thandithiols repeated. The purified product melts at 110 to 111 degrees C.

Example 3

3,3'-AHexamethylene bis (thiomethylene) _ / bis (6-t-butyl-2,4-dimethylphenol).

The procedure of Example 1 is repeated with 15 g (0.075 mol) of 1,6-hexanedithiol. The cleaned product melts at 134 to 135 degrees C.

Example 4

3,3 '- / ethylethylene-bis (thiomethylene) _ / bis (6-t-butyl-2,4-dimethylphenol),

The procedure of Example 1 is carried out with an equivalent amount (0.075 mol) of ethyl-1,2-ethandithiol

^1st Ptl

.CH ₂ «SH

Repeatedly instead of the ethanedithiol. The purified product is a pale yellow oil.

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Example 5

3,3 '- / jp-phenylene-bis (methylene thiomethylene) _ / bis- (6-tbuty 1-2, 4-dimethylphenol).

(CH,), G.

CH ₂ S-CH ₂

C (GH,).

(A) In a 200 ml three-necked flask containing ¹ IO ml of tert-butanol, are 9.25 g (0.08 mol) of potassium tert-butoxide and 18.5 g (0.08 mol) of tert-butyl-6-3 -mercaptomethyl-2,4-dimethylphenol given. 6.75 g (0.0375 mol) of alpha, alpha'-dichloro-p-xylene and 40 ml of dimethylformamide are added to this mixture while stirring. The reaction mixture is heated to 100 to 104 degrees for 3 1/2 hours and concentrated in vacuo. The residue is added to 200 ml of ice water, whereby 20.95 g of a sticky yellow precipitate are obtained. Recrystallization from a mixture of benzene and methylcyclohexane (1: 1) gives fine brownish crystals with a melting point of 183 to 185 degrees. After two more recrystallizations from a mixture of chloroform and methanol (1: 2), an analytically pure sample with a melting point of 195 to 196 degrees is obtained.

calc .: S 11.64;

found: S 11.06

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- ¹¹ - 21Ü298A

(b) In the same way, by using 1,4-dichloromethyldurol instead of alpha, alpha ^1- dichloro-pxylene, the following compound is prepared.

3,3 '- / tetramethyl-p-phenylene-bis (methylene) _ / bis- (6-t-butyl-2,4-dimethylphenol).

R = t-butyl; Y = CH ₂

-; n = 2

Example 6

2,4-tris? / (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) thio __ / methyl j mesitylene.

OH

- GH

• z.

CH ₂ S.CH ₂

"NS

109831/2261

Into a 500 ml three-necked flask fitted with a Dean-Stark trap is equipped and contains 200 ml of methyl isobutyl ketone, 11 g (0.04 mol) of 3-acetoxy-4-tert-butyl-2,6-dimethylbenzyl mercaptan, 3 g (0.0075 mol) of 2,4,6-tribromoethylmesitylene, 5.52 g (0.04 mol) of anhydrous Potassium carbonate and 1 g (0.006 mol) potassium iodide. The mixture is refluxed for 6 hours heated and then cooled. The inorganic salts are filtered off and the solvent is evaporated driven off, whereby a semi-solid residue is obtained. By extracting with benzene, washing and Concentration gives 10.6 g of a viscous residue. The product 2,4,6-tris / / (3-acetoxy-iJ-tert-butyl-2,6-dimethylbenzyl) thio_ / methylj Mesitylene is obtained by chromatography on aluminum oxide using a mixture of hexane and chloroform (1: 1) isolated as an eluent in the form of an oil.

The oily product is hydrolyzed with aqueous alcoholic potassium hydroxide under nitrogen. Recrystallize from chloroform provides an analytically pure sample with a melting point of 193 to 196 degrees.

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Example 7 Bis / 2- (4-t- "butyl-3-hydroxy-2,6-dimethylbenzylthio) -

ät hy l_ / t e r e ph t hala t

(H, C)

'S * CH ₂ CH ₂ OH + Cl-C

C-Cl

OH

189 g (0.83 mol) of 6-tert-butyl-3-chloromethyl-2,4-dimethylphenol, 65 g (0.83 mol) of 2-mercaptoethanol, 115 g (0.83 mol) of anhydrous potassium carbonate and 2 g (0.012 mol) of potassium iodide were added. The mixture is heated to reflux temperature with stirring until the azeotropic distillation ceases. Then the mixture is cooled to 50 degrees and added to 750 ml of 0.6l η hydrochloric acid. The organic layer is separated and washed four times with 200 ml of water each time. After removing the solvent by distillation in vacuo, 217 g (97 %) of an oily residue are obtained.

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- Ill -

A solution of 15.82 g (0.20 mole) of terephthaloyl chloride in 30 ml of chloroform is prepared slowly with stirring to a mixture of 33, ¹ I g (0.125 mol) of the above 6-tert-butyl-3 - / (2 -hydroxyäthylthio) methyl _ / - 2,4-dimethylphenols and 15.82 g (0.20 mol) of pyridine in 130 ml of chloroform. The reaction mixture is heated to 35 to 40 degrees for 17 1/2 hours and then cooled. The chloroform solution is washed four times with 50 ml of water each time, dried over anhydrous sodium sulfate and concentrated in vacuo to give 44 g of a sticky residue.

Repeated recrystallization from methanol or chloroform results in an analytically pure sample of colorless Crystals with a melting point of 142 to 145 degrees.

Calculated: C 68.47; H 7.51; S 9.61 Measured values: C 68.47; H 6.62; S 9.58

Example 8

BisM-t-butyl-3-hydroxy-2,6-dimethylbenzyl) thio_ / ethyl adipate

OH

H ₃ C

S.CH ₂ CH ₂ O.CO. (CH ₂

0.OH ₂ CH ₂ .S.CH ₂ -

C (CH,)

H.

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A mixture of 26.8 g (0.10 mol) of the 6-tert-butyl-3- / _> (2-hydroxyethylthio) methyl / 2,4-dimethylphenol prepared according to Example 1 and 7.91 g (0.10 mol ) Pyridine in 100 ml of tetrahydrofuran is mixed with a solution of 8.25 g (0.045 mol) of adipoyl chloride in 45 ml of tetrahydrofuran. The mixture is left to react for 18 hours at 30 to 35 degrees. The pyridine hydrochloride formed (9.35 g, theoretically 10.1J g) is filtered off. The piltrate is concentrated to 50 ml and added to 200 ml of cold water, whereby an oily precipitate forms, which is taken up in 200 ml of benzene. The benzene solution is washed with $ 15 saline, dried over anhydrous sodium hydroxide, and concentrated to give 27.0 g of an oil. The product is purified by repeated chromatography on silica gel with CHCl, ethyl acetate (1: 1), benzene / ethyl acetate (1: 2) or benzene. Repeated chromatography on aluminum oxide with hexane / ethyl acetate (2: 1) gives a sample whose NMR spectrum confirms the structure ascribed to the desired compound.

Example 9

Bis / 4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) thio_ / ethyl succinate

The procedure of Example 8 is carried out with 6.97 g (0.45 mol) Repeated succinyl chloride instead of Adlpoylchlorids. The product is purified by chromatography and obtained in the form of a viscous oil.

109831 / ?? 51

Example 10

Tetrakis _: / 2- ( ⁱ lt-butyl-3-hydroxy-2,6-dimethylbenzyl-thio) ethyl_ / pyromellitate.

(H ₃ G) ₃ C

OHi

.S.CH ₂ GH ₂ O.GO

^C 6 ^H 2

A mixture of 27 g (0.10 mol) 6-tert-butyl-3- / _ ( 2-hydroxy-ethylthio) methyl _ / -2, iJ-dimethylphenol and 12.6 g (0.16 mol) pyridine in 130 ml of tetrahydrofuran is added a solution of 6.6 g (0.02 mol) Pyro ^me llithoylchlorid in 100 ml of tetrahydrofuran. The reaction mixture is stirred for 12 hours at a temperature of 30 to 35 degrees and acidified with hydrochloric acid. Evaporation of the solvent gives an oily residue which is taken up in 300 ml of benzene. The benzene solution is washed with water, dried over anhydrous sodium sulfate and concentrated to 37 g of an oily residue. This is purified by chromatography on aluminum oxide with hexane / ethyl acetate (1: 2), whereby a yellow oil is obtained. The structure of this product is confirmed by the NMR spectrum.

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Example 11

Bis / _2- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzylthio) ■ ethyl _ / - 2,5-dimethyl terephthalate

OH

(H ₃ C) ₃ G

OH ₂ .S.GH ₂ GH ₂ O.GO

GH

• G ₆ H ₂ (GH ₃ ) ₂

This compound is made according to the procedure of Example 10 with the equivalent amount of 2,5-dimethylterephthaloyl chloride obtained instead of the pyromellithoyl chloride.

Example 12

Bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol adipate

(H ₃ C) ₃ G

OH

GH,

CH ₂ .S.CO.

CH,

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26.88 g (0.12 mol) of 3-hydroxy-2,6-dimethyl-4-tert-butyl-benzyl mercaptan are placed in a 500 ml three-necked flask and 11.86 g (0.15 mol) of pyridine in 115 ml of tetrahydrofuran. The mixture is slowly stirred, which is continued for 22 hours at about 25 to 35 degrees C with a solution of 9.15 g (0.05 mol) of adipoyl chloride added in 25 ml of tetrahydrofuran.

4.2 ml of concentrated hydrochloric acid are diluted with 200 ml of water and added to the reaction mixture, which then is extracted twice with 100 ml of benzene each time. The benzene extracts are combined, washed twice with water and concentrated to a syrupy residue. The product is purified by chromatography on silica gel obtained with chloroform / ethyl acetate in the form of colorless crystals.

Example 13

Bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -3,3-thiobis- (thiopropionate)

OH

CH

3 ^J Y \ -CO.CH ₂ CH ₂ .S.CH ₂ CH ₂ .CO.S.CH ₂ 1 \

CH ₃

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26.88 g (0.12 mol) of 3-hydroxy-2,6-dimethyl-4-tert-butylbenzyl mercaptan and Added 11.86 g (0.15 mol) of pyridine in 115 ml of tetrahydrofuran. The mixture slowly becomes one with stirring Solution of 10.75 g (0.05 mol) of 3,3'-thiodipropionyl chloride added in 20 ml of tetrahydrofuran. The reaction mixture is at a temperature of 30 to 21 hours Stirred at 35 degrees.

4.2 ml of concentrated hydrochloric acid are added to the reaction mixture and diluted by addition of 200 ml kai \ tem water. The aqueous solution is extracted twice with 100 ml of benzene each time. The benzene solution is washed twice with 100 ml of water each time and concentrated to 38 g of a syrupy residue.

The product is chromatographed on silica gel with chloroform / ethyl acetate (4: 1) and then Purified chromatography on silica gel with benzene as the eluent. Recrystallization from benzene provides an analytically pure sample of colorless crystals with a melting point of 124 to 125 degrees.

Calculated: C 65.08; H 7.80; S 16.27 j

Found: C, 65.27; H 8.13; S 16.22

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Example 14

Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate

(CH,), C.

y y

C-S-CH

A solution of 8.12 g (0.04 mol) of terephthaloyl chloride in 40 ml of benzene is slowly stirred into a Mixture of 22.4 g (0.10 mol) 6-tert-butyl-3-hydroxy-2,6-dimethylbenzyl mercaptan, 39.6 g (0.50 mol) of pyridine and 45 ml of benzene were added. The implementation will Performed for 12 hours at a temperature of 39 to 42 degrees.

The reaction mixture is added to 250 ml of ice water containing 35 ml (0.42 mol) of concentrated hydrochloric acid. The resulting yellow oily precipitate is extracted with 250 ml of benzene. The benzene solution is washed twice with 100 ml of water each time, dried over anhydrous sodium sulfate and concentrated to 25 g of crystals. The crude product is recrystallized from hexane / benzene / acetonitrile (11: 6: 1) to give 12.98 g of cream-colored crystals with a melting point of 208 to 212 degrees. One

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further recrystallization from benzene / hexane (1: 2) provides an analytically pure sample with a melting point 215 to 218 degrees.

Calculated: C 70.59; H 7.27; S 11.07 Measured values: C 70.14; H 7.24; S 10.75

(H ₃ C) ₃ O

Example 15

1,3,4-thiodiazole-2, 5-bis (3,3'-thiomethylene-2,4-dimethyl-6-t-butylphenol)

C (CH ₃ ) ₃

A mixture of 22.65 g (0.10 mol) of 3-hydroxy-2,6-dimethyl-4-tert-butylbenzyl chloride, 7.51 g (0.05 mol) 2,5-dimercapto-1,3,4-thiadiazole, 13.8 g (0.10 mol) anhydrous potassium carbonate and 0.5 g of potassium iodide in 250 ml of methyl isobutyl ketone is placed in a 500 ml three-necked flask, which is equipped with a Dean-Stark water separator, with stirring for 2 1/2 hours heated to reflux temperature.

After the reaction mixture has cooled, the crystalline mass is filtered off, washed with water and in vacuo

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dried to give 19.85 g of crystals having a melting point of 223 to 225 degrees. Another Product fraction of 2 g is isolated from the mother liquor.

Recrystallization from benzene and from chloroform provides an analytically pure sample with a melting point of 230 bis Degree.

Calcd .: C 63.50; H 7.17; N 5.28; S 18.11 Measured values: C 61.72; H 7.08; N 5.01; S 18.65

The assigned structure is indicated by the NMR spectrum confirmed.

Example 16

The compound of Example 15 is in unstabilized polypropylene in an amount of 0.2% _t based on the weight of the polymer, introduced by rolling at 175 to 180 ° C. The polypropylene is then compression molded into a film 0.38 to 0.51 mm (15 to 20 mils) thick. This is aged in a forced air oven at 1 * 10 degrees C together with other films made of the same polypropylene that does not contain any antioxidants. The effectiveness of the compound is determined by determining the time taken for embrittlement at this temperature.

The polypropylene film containing the compound of Example can withstand 725 to 750 hours of heating,

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before it becomes brittle, while the control film reaches its brittleness point after 2 to 4 hours achieved.

Example 17

The compounds of the previous examples are in unstabilized polypropylene in amounts of 0.2? based on the weight of the polymer, introduced by rolling at 175 to 180 degrees. Then the Polypropylene produced by compression molding films 0.38 to 0.51 mm (15 to 20 mils) thick. These

Slides are placed in a forced air oven at 1 * 10 degrees C j

aged. The effectiveness of the connection in question "

as an antioxidant is determined by the time in hours until embrittlement at this temperature is detected. The results are shown as follows

Tabel Tabel

Hours to the additive brittleness point

none (control) 2-4

Example 1 230-235

Example 2 310-320

Example 3 490-500

Example 4 370-380 j

Example 5 (a) 550-560

Example 6 240-250

Example 7 540-550

Example 8 "390-410

Example 10 130-140

Example 13 970-990

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These results show that the effectiveness of the inventive Compounds used as antioxidants increases when the molecular weight of the hydrocarbon bridge forms a major proportion of the total molecular weight of the compound. This is very surprising since the antioxidant activity is usually attributed to the phenolic portion of the molecule.

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Claims (13)

Claim e Thiomethylene phenol compounds by the formula wherein R is a branched alkyl radical having 3 to 12 carbon atoms, Y is a divalent or trivalent Hydrocarbon group with 2 to about 20 carbon atoms, the remainder of an organic polycarboxylic acid with 2 to about 14 carbon atoms, or the group N - N - C η is an integer from 2 to 4, χ 0 or 1, and ζ 0 or 1, where z, when χ 0 is also 0 and where χ and ζ are 0 when Y is the group N N Il Il means. 109831/2251 2. thiomethylene phenol according to claim 1, characterized by the formula OH OH CH CH ₂ S-Y'-SGH ₂ CH, where R is a branched alkyl radical having 3 to 12 carbon atoms and Y ^{1 is} a hydrocarbon radical having 2 to about 20 carbon atoms. 3. thiomethylene phenol according to claim 2, characterized in that Y ¹ means. 4. thiomethylene phenol according to claim 1, characterized by the formula CH ₂ S.CH 109831/2251 wherein R is a branched alkyl radical with 3 to 12 carbon atoms, R ₁ , R _? and R, hydrogen atoms or alkyl radicals having 1 to 3 carbon atoms and XR ₁ or the radical OH »SCHp mean. OH, 5. thiomethylene phenol according to claim 4, characterized by the formula OH OH H, C __ CH ₂ S CH, CH, - wherein R is a branched alkyl radical having 3 to 12 carbon atoms means. 6. thiomethylene phenol with a dicarboxylic acid bridge according to claim 1, characterized by the formula 109831/7251 CH ₃ .S OH ₂ CH ₂ O) J ₅ -CO. Y. CO GH wherein R is a branched alkyl radical with 3 to 12 carbon atoms, ζ 0 or 1, and Y denotes the residue of an organic dicarboxylic acid. 7. A compound according to claim 6, characterized by the formula GH CH ₂ .S.CO.Y.GO.S.CH ₂ wherein R is a branched alkyl radical having 3 to 12 carbon atoms and Y the group means. 109831 8. A compound according to claim 6, characterized in that that ζ O and Y the group - CHp CHp S CHp CHp- means. 9 · Compound according to claim 1, characterized by the formula Η, σ NS, CH, ιί: ι wherein R is a tertiary alkyl radical having 4 to 12 carbon atoms means. 10 Organic material exposed to oxidative degradation, characterized in that it contains a thiomethylene phenol according to claim 1 as an antioxidant. 11. Oxidative degradation exposed polyolefin, characterized in that it contains a thiomethylene phenol according to claim 1 as an antioxidant « BATH ORIGINAL 10SI31 / 2251 12. Polypropylene exposed to oxidative degradation, characterized in that it is a thiomethylene phenol naoh claim 1 contains as an antioxidant. 13. Use of a thiomethylene phenol according to claim 1 as an antioxidant in substrates that are exposed to the degrading effects of oxygen. 10M31 / 2251