EP0271437B1 - Sulphurized lubricant additives - Google Patents

Description

The present invention relates to lubricant additives containing substituted thio-thiophene derivatives and new substituted thio-thiophene derivatives.

Lubricants are generally added to improve performance. Special requirements with regard to the load carrying capacity are placed on lubricants for the transmission of larger forces. By adding high-pressure and wear-reducing additives, the otherwise occurring negative phenomena are greatly reduced.

DE-OS 2 242 637 describes thio-thiophthenes substituted by hydrocarbon groups, which are used as oxidation inhibitors in lubricants.

worin beide R¹ unabhängig voneinander ein Wasserstoffatom, ein Metallkation, NH₄⊕, primäres, sekundäres, tertiäres oder quaternäres Ammonium, lineares oder verzweigtes C₁-C₂₄-Alkyl, gegebenenfalls durch C₁-C₁₈-Alkyl substituiertes Cycloalkyl oder Cycloalkylalkyl mit 3 bis 7 Ring-C-Atomen, C₇-C₁₆- ⊕ Aralkyl oder C₈-C₄₀-Alkaralkyl bedeuten, wobei das C₁-C₂₄-Alkyl durch -NR4R5 , - NR⁴R⁵R⁶ , -OR7 , -SR⁷ , -(C_mH_2mO)_nR⁸ , -C(0)OR⁹ , oder C₁-C₂₀-Acyloxy substituiert sein kann, worin R⁴, R⁵ und R⁶ unabhängig voneinander ein Wasserstoffatom, gegebenenfalls durch -OH substituiertes, C₁-C₂₀-Alkyl oder R⁴ und R5 zusammen Tetramethylen, Pentamethylen oder 3-Oxapentylen, R7 ein Wasserstoffatom, lineares oder verzweigtes C₁-C₁₈-Alkyl, gegebenenfalls durch C₁-C₁₂-Alkyl substituiertes Cyclohexyl, Phenyl oder Benzyl, R⁸ ein Wasserstoffatom, C₁-C₁₈-Alkyl oder C₁-C₂₀-Acyl, und R⁹ ein Wasserstoffatom, der um eine Hydroxylgruppe verminderte Rest eines einwertigen Alkohols, ein Metallkation, NH_4⊕ oder primäres, sekundäres, tertiäres oder quaternäres Ammonium sind, m für eine ganze Zahl von 1 bis 6 und n für eine Zahl von 1 bis 20 stehen,

• R² und R³ unabhängig voneinander ein Wasserstoffatom, lineares oder verzweigtes C₁-C₂₀-Alkyl darstellen, oder R2 und R3 zusammen -CpH₂p-bedeuten, worin p für eine ganze Zahl von 2 bis 9 steht.

An object of the present invention is a composition containing a lubricant or a hydraulic fluid and at least one compound of the formula

wherein both R ¹ independently of one another are a hydrogen atom, a metal cation, NH ₄ ⊕, primary, secondary, tertiary or quaternary ammonium, linear or branched C ₁ -C ₂₄ alkyl, cycloalkyl or cycloalkylalkyl optionally substituted by C ₁ -C ₁₈ alkyl 3 to 7 ring C atoms, C ₇ -C ₁₆ - ⊕ aralkyl or C ₈ -C ₄₀ -alkaralkyl, the C ₁ -C ₂₄ -alkyl being represented by -NR4R5, - NR ⁴ R ⁵ R ⁶ , -OR7 , -SR ⁷ , - (C _m H _2m O) _n R ⁸ , -C (0) OR ⁹ , or C ₁ -C ₂₀ acyloxy, in which R ⁴ , R ⁵ and R ⁶ independently of one another are a hydrogen atom , optionally substituted by -OH, C ₁ -C ₂₀ alkyl or R ⁴ and R5 together tetramethylene, pentamethylene or 3-oxapentylene, R7 is a hydrogen atom, linear or branched C ₁ -C ₁₈ alkyl, optionally by C ₁ -C ₁₂ -Alkyl substituted cyclohexyl, phenyl or benzyl, R ^{8 is} a hydrogen atom, C ₁ -C ₁₈ alkyl or C ₁ -C ₂₀ acyl, and R ^{9 is} a hydrogen atom which is surrounded by a hydroxyl group v reduced residue of a monohydric alcohol, a metal cation, NH _4⊕ or primary, secondary, tertiary or quaternary ammonium, m stand for an integer from 1 to 6 and n stand for a number from 1 to 20,

• R ² and R ³ independently of one another represent a hydrogen atom, linear or branched C ₁ -C ₂₀ alkyl, or R2 and R3 together mean -CpH ₂ p-where p is an integer from 2 to 9.

If R ^{1 represents} a metal cation, then it is preferably an alkali, alkaline earth or transition metal cation. Zn ²⁺ and C _U ²⁺ are particularly preferred among the transition metal cations. Li⊕, Nae, K⊕, Mg ²⁺ and Ca ^{2+ are} preferred among the alkali and alkaline earth metal cations. In a preferred subgroup, both represent R ¹ H, NH _4⊕ , Lie, Nae, K _⊕ , Mge, C _a⊕ , Zn ²⁺ and C _U ²⁺ .

oder R¹⁰R¹¹R¹²R¹³N⊕ worin R¹⁰, R¹¹, R12 und R13 unabhängig voneinander gegebenenfalls durch Hydroxyl substituiertes, lineares oder verzweigtes C₁-C₁₈-Alkyl, besonders C₁-C₁₂-Alkyl und insbesondere C₁-C₆-Alkyl sind. In wässrigen oder wässrig-organischen Substraten werden zweckmässig aus Gründen der Löslichkeit solche Ammoniumverbindungen verwendet, in denen R¹⁰, R¹¹, R¹² und R13 gegebenenfalls durch Hydroxyl substituiertes C₁-C₄-Alkyl darstellen. In organischen Substraten werden zweckmässig solche Ammoniumverbindungen verwendet, in denen das N-Atom durch wenigstens eine langkettige, z.B. 6-20 C-Atome enthaltende Alkylgruppe substituiert ist. Eine bevorzugte Gruppe solcher Ammoniumverbindungen ist jene, worin in den zuvor angegebenen Formeln R¹⁰ lineares oder verzweigtes C₆-C₁₈-Alkyl und R¹¹, R¹² und R¹³ lineares oder verzweigtes C₁-C₄-Alkyl sind.R1 in the meaning of primary, secondary, tertiary and quaternary ammonium can contain 1 to 40, preferably 1 to 30, carbon atoms. The N atoms can be substituted with cyclo-substituted, linear or branched C ₁ -C ₂₀ -alkyl, optionally C ₁ -C ₆ -alkyl-substituted cycloalkyl or cycloalkyl-C ₁ -C ₂ -alkyl with 4 to 7 ring-C- Atoms, C ₁ -C ₁₂ alkyl substituted phenyl, benzyl or phenylethyl, or by optionally C ₁ -C ₄ alkyl substituted tri- or tetramethylene or 3-oxapentylene. Both R ¹ in formula I in the meaning of ammonium preferably correspond to the formulas

or R ¹⁰ R ¹¹ R ¹² R ¹³ N⊕ in which R ¹⁰ , R ¹¹ , R12 and R13 independently of one another, optionally substituted by hydroxyl, linear or branched C ₁ -C ₁₈ alkyl, especially C ₁ -C ₁₂ alkyl and in particular C Are ₁ -C ₆ alkyl. For reasons of solubility, such ammonium compounds are expediently used in aqueous or aqueous-organic substrates in which R ¹⁰ , R ¹¹ , R ¹² and R 13 are C ₁ -C ₄ alkyl optionally substituted by hydroxyl. Such organic compounds are expediently used in organic substrates in which the N atom is substituted by at least one long-chain alkyl group containing, for example, 6-20 C atoms. A preferred group of such ammonium compounds is that in which, in the formulas given above, R ^{10 is} linear or branched C ₆ -C ₁₈ alkyl and R ¹¹ , R ¹² and R ^{13 are} linear or branched C ₁ -C ₄ alkyl.

Some examples of R ¹ in the meaning of ammonium are: methyl, ethyl, n and i-propyl, n, i and t-butyl, pentyl, hexyl, heptyl, octyl, nonyl -, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, hydroxyethyl, 2-hydroxypropyl, dimethyl, (methyl) (ethyl), diethyl, dihydroxyethyl, dibutyl , (Methyl) (butyl) -, (methyl) (hexyl) -, (methyl) (dodecyl) -, (methyl) (octadecyl), trimethyl, triethyl, trihydroxyethyl, tri-n-butyl, (hexyl ) (Dimethyl) -, (Octyl) (Dimethyl) -, (Dodecyl) (Dimethyl) -, (Octadecyl) (Dimethyl) -, Tetramethyl-, Tetraethyl-, Tetrabutyl-, (Trimethyl) ethyl-, (Dimethyl) (Dibutyl ) -, (Trimethyl) (Hexyl) -, (Trimethyl) (Dodecyl) -, (Trimethyl) (Octadecyl) -, Cyclohexyl-, (Cyclohexyl) (Dimethyl) -, Cyclohexyl (Trimethyl) -, (Cyclohexyl) methyl-, (Methylphenyl) -, (Phenyl) (Dimethyl) -, (Methylbenzyl) -, (Methyl) (Benzyl) -, (Benzyl) Dimethyl-, (Dimethylbenzyl) -, (Nonylphenyl) -, (Decylphenyl) -, (dodecylphenyl) -, (octadecylphenyl) -, (decylphenyl) (dimethyl) ammonium.

If R ^{1 represents} unsubstituted alkyl, it is preferably linear or branched Ci-C ₂₀ -, especially C ₂ -C ₁₈ -, in particular C ₂ -C ₁₂ - and very particularly C ₄ -C ₁₂ alkyl. Examples of alkyl are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, n-pentyl, 2-methylbut-1-yl, n-hexyl-, 2-methylpent-1- yl, 2-ethylpent-1- or -2-yl, n-heptyl, 2-n-propylhept-1-yl, n-octyl, 2-ethylhex-1-yl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, hexadecyl, octadecyl and eicosyl.

Ri in the meaning of aralkyl, preferably phenylalkyl, contains in particular 7 to 12 carbon atoms and is particularly benzyl, 1-phenyleth-2-yl, 1-phenyleth-1-yl, 1-phenyl-prop-1-, -2 - or -3-yl.

If R ^{1 represents} alkaralkyl, its aryl group is preferably phenyl and its alkylene group is preferably 1,1- or 1,2-ethylene and especially methylene. The alkaralkyl preferably contains 1 to 3, in particular 1 or 2, alkyl groups which preferably contain 1 to 20, in particular 1 to 12, carbon atoms and can be linear or branched. In particular, R ¹ as alkaralkyl represents mono- or dialkylbenzyl having 8 to 20 carbon atoms. Examples of alkaralkyl are methylbenzyl, 1- (methylphenyl) eth-2-yl, dimethylbenzyl, ethylbenzyl, n- or i-propylbenzyl, n- or t-butylbenzyl, di-t-butylbenzyl, hexylbenzyl, octylbenzyl, methylbutylbenzyl, nonylbenzyl, dioctyl or dinonylbenzyl, decylbenzyl, dodecylbenzyl, hexadecylbenzyl, octadecylbenzyl.

If R ^{1 represents} cycloalkyl or cycloalkylalkyl, the cycloalkyl groups are preferably cyclopentyl and especially cyclohexyl. The alkylene group in cycloalkylalkyl is preferably ethylene and especially methylene. If the cycloalkyl groups are substituted by alkyl, the alkyl preferably contains 1 to 12 and in particular 1 to 6 carbon atoms. The alkyl can be linear or branched. Some examples are methyl, dimethyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 3,3,5-trimethylcyclohexyl, decylcyclohexyl or cyclopentyl, (methylcyclohexyl) methyl, cyclopentylmethyl, cyclohexylmethyl.

R ¹ can be substituted as alkyl as previously defined. In this case, the alkyl preferably contains 1 to 12, particularly 1 to 6, and in particular 1 to 3 carbon atoms.

In the meaning of alkyl, R ¹ can be substituted by amino or ammonium groups of the formulas -NR4R5 or - ⊕ NR4R5R6, in which R4, R5 and R6 independently, preferably for a hydrogen atom or optionally substituted by -OH, C ₁ -C ₁₈ -, especially C ₁ -C ₁₂ - and in particular C ₁ -C ₆ alkyl. In aqueous or aqueous-organic substrates, such compounds of formula I are conveniently used in which R4 is R5 or R6, if appropriate, particularly C ₁ -C, through -OH-substituted C ₁ -C ₆ .- ₄ alkyl or a hydrogen atom. In organic substrates such compounds of formula I are advantageously used, in which R 4 is C ₆ -C ₁₈ alkyl, and R5 and R6 independently represent a hydrogen atom or C ₁ -C ₆ -, especially C ₁ -C ₄ represent alkyl. Examples of alkyl groups have previously been listed for R1 in the meaning of ammonium.

In the meaning of alkyl, R ¹ can be substituted by -OR ⁷ or -SR ⁷ . R ⁷ is preferably a hydrogen atom, linear or branched C ₁ -C ₁₂ -, especially C ₁ -C ₆ -alkyl, cyclohexyl optionally substituted by C ₁ -C ₄ -alkyl, or optionally by Ci-C ₁₈ -, especially C ₁ -C ₁₂ alkyl substituted phenyl or benzyl. Examples of such alkyl groups have previously been listed for R ¹ in the meaning of alkyl substituted cycloalkyl and alkaralkyl. Examples of R ⁷ as alkylphenyl are methyl-, dimethyl-, ethyl-, n- or i-propyl-, n-, i- or -t-butyl-, methyl-t-butyl-, di-t-butyl-, Pentyl, hexyl, octyl, dioctyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, dinonyl, didecyl and didodecylphenyl.

If R ¹ represents alkyl substituted by acyloxy, the acyloxy preferably contains 1 to 12 and in particular 1 to 6 carbon atoms. Examples of acyloxy are formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, cyclohexanoyl, octanoyl, decanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl and benzoyloxy.

substituiert sein. In der Formel bedeutet m bevorzugt eine ganze Zahl von 1 bis 4 und n eine Zahl von 1 bis 12, besonders 1 bis 6. R⁸ in der Bedeutung von Alkyl und Acyl enthält bevorzugt 1 bis 12, besonders 1 bis 6 C-Atome. Beispiele für Alkyl und Acyl sind zuvor aufgezählt worden. Beispiele für die CmH2m-Gruppe sind Ethylen, 1,2- oder 1,3-Propylen, 1,2-, 1,3- oder 1,4-Butylen, 1,5-Pentylen und 1,6-Hexylen.R ¹ can be alkyl through the group of formula

be substituted. In the formula, m preferably denotes an integer from 1 to 4 and n denotes a number from 1 to 12, particularly 1 to 6. R ⁸ in the meaning of alkyl and acyl preferably contains 1 to 12, particularly 1 to 6, carbon atoms. Examples of alkyl and acyl have been enumerated previously. Examples of the CmH2m group are ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene and 1,6-hexylene.

R ¹ in the meaning of alkyl can be substituted by the group -C (O) OR ⁹ . For R9 in the meaning of metal cation and ammonium, the preferences given for R1 in this meaning apply. R ⁹ as the residue of a monohydric alcohol preferably contains 1 to 18, particularly 1 to 12 and in particular 1 to 8 carbon atoms. It can be the remainder of an aromatic and especially aliphatic alcohol. R ⁹ can be, for example, linear or branched C ₁ -C ₂₀ -, preferably C ₁ -C ₁₈ - and especially C ₁ -C ₁₂ alkyl, or optionally substituted by C ₁ -C ₁₂ -, especially C ₁ -C ₆ alkyl Cyclohexyl, cyclopentyl, (cyclohexyl) methyl, phenyl or benzyl. Examples of such residues have been listed above. A preferred embodiment of the invention is characterized in that in formula I both R ¹ are C ₁ -C ₆ alkyl substituted by -C (O) OR ⁹ , in which R ^{9 has} the meaning given above. A particularly preferred embodiment of the invention is characterized in that both R ¹ correspond to the radical of the formula -CH ₂ C (O) OR ⁹ , in which R9 is H, NH _4β , a metal cation, primary, secondary, tertiary or quaternary ammonium or C ₁ -C ₂₀ alkyl.

If R ² and R ^{3 are} alkyl, it preferably contains 1 to 12, especially 1 to 6, carbon atoms. Examples of alkyl have been enumerated previously. In the group -CpH ₂ p- p is preferably an integer from 2 to 5, particularly 2 or 3 and in particular 3. Examples of the group -CpH ₂ p- are ethylene, 1,2- or 1,3-propylene , 1,4-butylene, 1,5-pentylene, 2-methyl-1,3-propylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene.

In a preferred embodiment, R ² and R3 represent a hydrogen atom, C _i -C ₄ alkyl or R2 and R ³ together represent the group -CpH ₂ p-, where p is an integer from 2 to 5, especially 2 or 3 .

-C(O)OR⁹ oder C₁-C₁₂-Acyloxy substituiert sein kann, worin R4, R⁵ und R⁶ unabhängig voneinander ein Wasserstoffatom oder C₁-C₁₈-Alkyl, R⁷ ein Wasserstoffatom, lineares oder verzweigtes C₁-C₁₂-Alkyl oder gegebenenfalls durch C₁-C₁₂-Alkyl substituiertes Phenyl oder Benzyl, R⁸ ein Wasserstoffatom, C_l-C₁₂-Alkyl oder C₁-C₁₂-Acyl, und R9 ein Wasserstoffatom, der um eine Hydroxylgruppe verminderte Rest eines einwertigen Alkohols mit 1 bis 20 C-Atomen, sind, m für eine ganze Zahl von 1 bis 4, und n für eine Zahl von 1 bis 6 stehen,

• R² und R3 unabhängig voneinander ein Wasserstoffatom, lineares oder verzweigtes C₁-C₁₂-Alkyl oder R² und R³ zusammen -CpH₂p- darstellen, worin p für eine ganze Zahl von 2 bis 7 steht.

Another preferred embodiment of the invention is characterized in that in formula I both R ¹ independently of one another are a hydrogen atom, an alkali metal, alkaline earth metal or transition metal cation, NH _4S , primary, secondary, tertiary or quaternary ammonium with C ₁ -C ₁₈ alkyl groups represent linear or branched C ₁ -C ₁₂ alkyl, optionally substituted by C ₁ -C ₆ alkyl, cyclohexyl, C ₇ -C ₁₂ phenylalkyl or C ₈ -C ₃₀ alkylbenzyl, the C ₁ -C ₁₂ alkyl by -NR ⁴ R ⁵ or - ⊕ NR ⁴ R ⁵ R ⁶ , -OR7 -SR7,

-C (O) OR ⁹ or C ₁ -C ₁₂ acyloxy can be substituted, in which R4, R ⁵ and R ⁶ independently of one another are hydrogen or C ₁ -C ₁₈ alkyl, R ^{7 is} a hydrogen atom, linear or branched C ₁ -C ₁₂ alkyl or phenyl or benzyl optionally substituted by C ₁ -C ₁₂ alkyl, R ^{8 is} a hydrogen atom, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ acyl, and R9 is a hydrogen atom which is a hydroxyl group reduced residue of a monohydric alcohol having 1 to 20 carbon atoms, m is an integer from 1 to 4 and n is a number from 1 to 6,

• R ² and R3 independently of one another represent a hydrogen atom, linear or branched C ₁ -C ₁₂ alkyl or R ² and R ³ together -CpH ₂ p-, where p is an integer from 2 to 7.

worin beide R¹ unabhängig voneinander ein Wasserstoffatom, ein Metallkation, NH₄⊕, primäres, sekundäres, tertiäres oder quaternäres Ammonium, gegebenenfalls durch C₁-C₁₈-Alkyl substituiertes Cycloalkyl oder Cycloalkylalkyl mit 3 bis 7 Ring-C-Atomen, C₇-C₁₆-Aralkyl oder C₈-C₄₀-Alkaralkyl, lineares ⊕ oder verzweigtes C₃-C₂₄-Alkyl oder durch -NR⁴R⁵, -NR⁴R⁵R⁶, -OR⁷, -SR⁷, -(C_mH_2mO)_nR⁸, -C(O)OR⁹ oder C₁-C₂₀-Acyloxy substituiertes C₁-C₂₄-Alkyl bedeuten, worin R4, R5 und R6 unabhängig voneinander ein Wasserstoffatom, gegebenenfalls durch -OH substituiertes C₁-C₂₀-Alkyl oder R⁴ und R5 zusammen Tetramethylen, Pentamethylen oder 3-Oxapentylen, R⁷ ein Wasserstoffatom, lineares oder verzweigtes C₁-C₁₈-Alkyl, gegebenenfalls durch C₁-C₁₂-Alkyl substituiertes Cyclohexyl, Phenyl oder Benzyl, R⁹ ein Wasserstoffatom, C₁-C₁₈-Alkyl oder C₁-C₂₀-Acyl, und R9 ein Wasserstoffatom, der um eine Hydroxylgruppe verminderte Rest eines einwertigen Alkohols, ein Metallkation, NH_4⊕ oder primäres, sekundäres, tertiäres oder quaternäres Ammonium sind, m für eine ganze Zahl von 1-6 und n für eine Zahl von 1 bis 20 stehen, und

• R2 und R³ unabhängig voneinander ein Wasserstoffatom, lineares oder verzweigtes C₁-C₂o-Alkyl darstellen, oder R2 und R³ zusammen -CpH₂p- bedeuten, worin p für eine ganze Zahl von 2 bis 9 steht.

Another object of the invention are the new compounds of formula la

wherein both R ¹ independently of one another are a hydrogen atom, a metal cation, NH ₄ ⊕, primary, secondary, tertiary or quaternary ammonium, cycloalkyl or cycloalkylalkyl with 3 to 7 ring C atoms optionally substituted by C ₁ -C ₁₈ alkyl, C ₇ -C ₁₆ aralkyl or C ₈ -C ₄₀ alkaralkyl, linear ⊕ or branched C ₃ -C ₂₄ alkyl or by -NR ⁴ R ⁵ , -NR ⁴ R ⁵ R ⁶ , -OR ⁷ , -SR ⁷ , - (C _m H _2m O) _n R ⁸ , -C (O) OR ⁹ or C ₁ -C ₂₀ acyloxy substituted C ₁ -C ₂₄ alkyl, in which R4, R5 and R6 independently of one another are a hydrogen atom, optionally by - OH substituted C ₁ -C ₂₀ alkyl or R ⁴ and R5 together tetramethylene, pentamethylene or 3-oxapentylene, R ^{7 is} a hydrogen atom, linear or branched C ₁ -C ₁₈ alkyl, optionally substituted by C ₁ -C ₁₂ alkyl cyclohexyl , Phenyl or benzyl, R ^{9 is} a hydrogen atom, C ₁ -C ₁₈ alkyl or C ₁ -C ₂₀ acyl, and R9 is a hydrogen atom, the radical reduced by one hydroxyl group it is monohydric alcohol, a metal cation, NH _4⊕ or primary, secondary, tertiary or quaternary ammonium, m is an integer from 1-6 and n is a number from 1 to 20, and

• R2 and R ³ independently represent a hydrogen atom, linear or branched C ₁ -C ₂ o -alkyl, or R2 and R ³ together mean -CpH ₂ p-, where p is an integer from 2 to 9.

If R ¹ in formula la represents alkyl, it preferably contains 6 to 18, especially 6 to 12, carbon atoms. For the other meanings of R ¹ , R ² and R ³ in formula la, the same preferences apply as these meanings for R ⁱ , R ² and R ³ in formula I.

Some of the compounds of the formula I are known or can be prepared by known processes. Suitable methods are e.g. by C. Portail et al. in Bull. Soc. Chim. Fr., 1966 (10), pp. 3187-3189.

worin R² und R³ die in Formel I angegebene Bedeutung haben, in Gegenwart eines Alkalialkoholats mit CS₂ umsetzt und danach entweder die Verbindung der Formel I, worin beide Rⁱ ein Wasserstoffatom darstellen, isoliert, oder durch Umsetzung mit R'X, Verbindungen der Formel I herstellt, worin R1 die Bedeutung von R' hat, wobei R' wie für Rⁱ in Formel I definiertes unsubstituiertes oder substituiertes Alkyl, Cycloalkyl, Cycloalkylalkyl, Aralkyl oder Alkaralkyl ist und X für Cl, Br oder J steht.The compounds of formula I can be prepared, for example, by using a compound of formula II

wherein R ² and R ^{3 have} the meaning given in formula I, reacted with CS ₂ in the presence of an alkali alcoholate and then either isolated the compound of formula I, in which both R ^{i represent} a hydrogen atom, or by reaction with R'X, compounds of formula I, in which R1 has the meaning of R ', where R' is unsubstituted or substituted alkyl, cycloalkyl, cycloalkylalkyl, aralkyl or alkaralkyl as defined for R ⁱ in formula I and X represents Cl, Br or J.

The reaction can be carried out at temperatures from -20 _° C to 40 _° C. The reaction is expediently carried out in an inert solvent, for example aromatic hydrocarbons, such as benzene, toluene or xylene. The compounds can be isolated in the customary manner by hydrolysis of the reaction mixture with water, removal of the organic phase and subsequent distillation or crystallization.

Compounds of the formula I in which R ¹ and R ^{9 represent} a metal cation or ammonium can be prepared by known metal or ammonium bases with compounds of the formula I in which R ⁱ and R ⁹ in formula I represent a hydrogen atom, implements. This implementation can also take place in situ in lubricants and hydraulic fluids.

The compounds of the formula I are liquid compounds of different viscosities or crystalline compounds. Compared to thiothiophthenes substituted by hydrocarbon radicals, they have improved solubility in aqueous and organic substrates. In addition, the solubility can be influenced in a targeted manner by the choice of the group R ¹ and even water-soluble compounds can be provided, for example if R ¹ and R ^{9 are} a hydrogen atom, metal cation or ammonium. In the case of viscous representatives, dilution with, for example, a paraffin oil or a corresponding base oil offers an inexpensive form of confection. The compounds of the formula I are outstandingly suitable as additives for lubricants and hydraulic fluids. Another object of the invention is the use of the compounds of formula I as additives in lubricants and hydraulic fluids. The addition of the compounds according to the invention leads to an improvement in the performance properties. A surprising improvement in high-pressure and anti-wear properties is found for pure sulfur compounds. Since the compounds do not contain phosphorus, they are particularly suitable for motor oils, since damage to catalysts can be avoided. In aqueous systems, the absence of phosphorus means that there is less risk of attack by microorganisms.

The compounds of the formula I are advantageously added to the lubricants and hydraulic fluids in an amount of 0.01 to 10% by weight, preferably in an amount of 0.05 to 5% by weight, based on the lubricant or the hydraulic fluid. 0.1-2% by weight is advantageously used in organic systems and 0.05-5% by weight is advantageously used in aqueous systems.

Such lubrication and hydraulic systems can be polar or non-polar in nature. The selection criteria result from the solubility properties of the corresponding compounds.

The lubricants in question are familiar to the person skilled in the art and e.g. in the "Lubricant Pocket Book" (Hüthig Verlag, Heidelberg, 1974) or by D. Klamann in "Lubricants and Related Products", Verlag Chemie, Weinheim (1982).

In addition to mineral oils, e.g. Poly-a-olefins, lubricants based on esters, phosphates, glycols, polyglycols and polyalkylene glycols, as well as their mixtures with water, and water itself, which preferably also contains a thickener to increase the viscosity.

The lubricants can additionally contain other additives which are added in order to further improve the basic properties of lubricants; these include: antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents, thickeners, biocides, anti-foaming agents, demulsifiers and emulsifiers as well as other high-pressure additives and friction reducers.

The use of zinc dialkyldithiophosphates has proven to be particularly advantageous since the action of the compounds of the formula 1 can be increased considerably. Zinc dialkyldithiophosphates with 1 to 18 carbon atoms, especially 1-12 carbon atoms in the alkyl groups, are particularly suitable. It is expedient to add 0.01 to 15, in particular 0.1 to 10,% by weight of zinc dialkyldithiophosphate, based on the lubricant or the hydraulic fluid.

• 1. Alkvlierte Monophenole 2,6-Di-tert-butyl-4-methylphenol
• 2,6-Di-tert-butylphenol
• 2-tert-Butyl-4,6-dimethylphenol
• 2,6-Di-tert-butyl-4-ethylphenol
• 2,6-Di-tert-butyl-4-n-butylphenol
• 2,6-Di-tert-butyl-4-iso-butylphenol
• 2,6-Di-cyclopentyl-4-methylphenol
• 2-(α-Methylcyclohexyl)-4,6-dimethylphenol
• 2,6-Di-octadecyl-4-methylphenol
• 3. Hydroxylierte Thiodiphenvlether 2,2'-Thio-bis-(6-tert-butyl-4-methylphenol)
• 2,2'-Thio-bis-(4-octylphenoi)
• 4,4'-Thio-bis-(6-tert-butyl-3-methylphenol)
• 4,4'-Thio-bis-(6-tert-butyl-2-methylphenol)
• 4. Alkyliden-Bisphenole 2,2'-Methylen-bis-(6-tert-butyl-4-methylphenol)
• 2,2'-Methylen-bis-(6-tert-butyl-4-ethylphenol)
• 2,2'-Methylen-bis-[4-methyl-6-(a-methylcyclohexyl)-phenol]
• 2,2'-Methylen-bis-(4-methyl-6-cyclohexylphenol)
• 2,2'-Methylen-bis-(6-nonyl-4-methylphenol)
• 2,2'-Methylen-bis-(4,6-di-tert-butylphenol)
• 2,2'-Ethyliden-bis-(4,6-di-tert-butylphenol)
• 2,2'-Ethyliden-bis-(6-tert-butyl-4-iso-butylphenol
• 2,2'-Methylen-bis-[6-(a-methylbenzyl)-4-nonylphenol]
• 2,2'-Methylen-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]
• 4,4'-Methylen-bis-(2,6-di-tert-butylphenol)
• 4,4'-Methylen-bis-(6-tert-butyl-2-methylphenol)
• 1,1-Bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butan
• 2,6-Di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol
• 1,1,3-Tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutan
• 6. Acylaminophenole 4-Hydroxy-laurinsäureanilid
• 4-Hydroxy-stearinsäureanilid
• 2,4-Bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazin
• N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbaminsäureoctylester.
• 7. Ester der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)-propionsäure mit ein- oder mehrwertigen Alkoholen,
• wie z.B. mit
• MethanolDiethylenglycol
• OctadecanolTriethylenglycol
• 1,6-HexandiolPentaerythrit
• NeopentylglycolTris-hydroxyethyl-isocyanurat
• ThiodiethylenglycolDi-hydroxyethyl-oxalsäurediamid

Examples of phenolic antioxidants as additional additives are:

• 1. Alkalized monophenols 2,6-di-tert-butyl-4-methylphenol
• 2,6-di-tert-butylphenol
• 2-tert-butyl-4,6-dimethylphenol
• 2,6-di-tert-butyl-4-ethylphenol
• 2,6-di-tert-butyl-4-n-butylphenol
• 2,6-di-tert-butyl-4-iso-butylphenol
• 2,6-di-cyclopentyl-4-methylphenol
• 2- (α-methylcyclohexyl) -4,6-dimethylphenol
• 2,6-di-octadecyl-4-methylphenol
• 3. Hydroxylated thiodiphenyl ether 2,2'-thio-bis- (6-tert-butyl-4-methylphenol)
• 2,2'-thio-bis- (4-octylphenoi)
• 4,4'-thio-bis- (6-tert-butyl-3-methylphenol)
• 4,4'-thio-bis- (6-tert-butyl-2-methylphenol)
• 4. Alkylidene bisphenols 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol)
• 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol)
• 2,2'-methylene-bis- [4-methyl-6- (a-methylcyclohexyl) phenol]
• 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol)
• 2,2'-methylene-bis- (6-nonyl-4-methylphenol)
• 2,2'-methylene-bis- (4,6-di-tert-butylphenol)
• 2,2'-ethylidene-bis- (4,6-di-tert-butylphenol)
• 2,2'-ethylidene bis (6-tert-butyl-4-iso-butylphenol
• 2,2'-methylene-bis- [6- (a-methylbenzyl) -4-nonylphenol]
• 2,2'-methylene-bis- [6- (α, α-dimethylbenzyl) -4-nonylphenol]
• 4,4'-methylene-bis- (2,6-di-tert-butylphenol)
• 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol)
• 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane
• 2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol
• 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane
• 6. Acylaminophenols 4-hydroxy-lauric anilide
• 4-hydroxy stearic anilide
• 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine
• N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.
• 7. esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols,
• like with
• Methanol diethylene glycol
• Octadecanol triethylene glycol
• 1,6-hexanediol pentaerythritol
• Neopentyl glycol tris hydroxyethyl isocyanurate
• Thiodiethylene glycol di-hydroxyethyl oxalic acid diamide

8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, e.g. With

• Methanol diethylene glycol
• Octadecanol triethylene glycol

Examples of aminic antioxidants:

• N, N'-di-isopropyl-p-phenylenediamine
• N, N'-di-sec-butyl-p-phenylenediamine
• N, N'-bis (1,4-dimethylpentyl) p-phenylenediamine
• N, N'-bis (1-ethyl-3-methylpentyl) p-phenylenediamine
• N, N'-bis (1-methyl-heptyl) -p-phenylenediamine
• N, N'-diphenyl-p-phenylenediamine
• N, N'-di- (naphthyl-2) -p-phenylenediamine
• N-isopropyl-N'-phenyl-p-phenylenediamine
• N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine
• N- (1-methyl-heptyl) -N'-phenyl-p-phenylenediamine
• N-cyclohexyl-N'-phenyl-p-phenylenediamine
• 4- (p-toluenesulfonamido) diphenylamine
• N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine
• Diphenylamine
• 4-isopropoxy-diphenylamine
• N-phenyl-1-naphthylamine
• N-phenyl-2-naphthylamine
• octylated diphenylamine
• 4-n-butylaminophenol
• 4-butyrylamino-phenol
• 4-nonanoylamino-phenol
• 4-dodecanoylamino-phenol
• 4-octadecanoylamino-phenol
• Di- (4-methoxyphenyl) amine
• 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol
• 2,4'-diamino-diphenylmethane
• 4,4'-diamino-diphenylmethane
• N, N, N ', N'-tetramethyl-4,4'-diamino-diphenylmethane
• 1,2-di - [(2-methylphenyl) amino] ethane
• 1,2-di (phenylamino) propane
• (o-tolyl) biguanide
• Di- [4- (1 ', 3'-dimethylbutyl) phenyl) amine
• tert-octylated N-phenyl-1-naphthylamine
• Mixture of mono- and dialkylated tert-butyl / tert-octyldiphenyl amines.

Examples of metal passivators are:

• for copper, for example:
  Triazole, benzotriazole and their derivatives, 2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole, salicylidene propylene diamine, salts of salicylaminoguanidine.

Examples of rust inhibitors are:

• a) Organic acids, their esters, metal salts and anhydrides, e.g. N-oleoyl sarcosine, sorbitan mono-oleate, lead naphthenate, dodecenylsuccinic anhydride, alkenylsuccinic acid half-ester, 4-nonylphenoxyacetic acid.
• b) Nitrogen-containing compounds, e.g .:

• I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, e.g. oil-soluble alkylammonium carboxylates.

II. Heterocyclic compounds, e.g .:

• c) Phosphorhaltige Verbindungen, z.B.: Aminsalze von Phosphorsäurepartialestern.
• d) Schwefelhaltige Verbindungen, z.B.: Barium-dinonylnaphthalin-sulfonate, Calciumpetroleum-sulfonate.

Substituted imidazolines and oxazolines.

• c) phosphorus-containing compounds, for example: amine salts of phosphoric acid partial esters.
• d) Sulfur-containing compounds, for example: barium dinonylnaphthalene sulfonates, calcium petroleum sulfonates.

Examples of viscosity index improvers are:

Polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polybutenes, olefin copolymers, styrene / acrylate copolymers, styrene / butadiene copolymers.

Examples of pour point depressants are:

Polymethacrylate, alkylated naphthalene derivatives.

Examples of dispersants / detergents are:

Polybutenylsuccinic acid imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.

Examples of wear protection additives are:

Compounds containing sulfur and / or phosphorus and / or halogen, such as sulfurized vegetable oils, zinc dialkyl or zinc diaryl dithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl disulfides, carbamates.

The following examples explain the invention in more detail. Parts are parts by weight unless otherwise specified.

A) Manufacturing examples Examples 1-5:

und 12 Teilen CS₂ in 220 Teilen Toluol versetzt. Man lässt das Gemisch während 3 Stunden bei 20_°C stehen. Danach wird das Reaktionsgemisch bei 5_°C mit 40 Teilen Chloressigsäureethylester versetzt und weitere 3 Stunden stehen gelassen. Darauf werden 190 Teile Wasser zugegeben, die organische von der wässrigen Phase abgetrennt und die wässrige Phase mit Toluol extrahiert. Die kombinierten organischen Phasen werden mit Wasser gewaschen und mit MgS0₄ getrocknet. Das erhaltene Rohprodukt (60 Teile) wird aus einer 2:1-Mischung von Toluol/Cyclohexan umkristallisiert.A suspension of 35 parts of sodium tertiary amylate (prepared by dissolving Na or NaH in t-amyl alcohol) in 220 parts of toluene is dissolved at 0 _° C. with a solution of 30 parts of 8,9-dithia-bicyclo- [4.3.0] _A 1, 6-nonen-7-thione of the formula

and 12 parts of CS ₂ in 220 parts of toluene. The mixture is allowed to stand at 20 _° C for 3 hours. The reaction mixture is then mixed with 40 parts of ethyl chloroacetate at 5 _° C. and left to stand for a further 3 hours. 190 parts of water are then added, the organic phase is separated from the aqueous phase and the aqueous phase is extracted with toluene. The combined organic phases are washed with water and dried with MgS0 ₄ . The crude product obtained (60 parts) is recrystallized from a 2: 1 mixture of toluene / cyclohexane.

Examples 2-5:

ersetzt. Die Verbindung der Beispiel 3 ist ein Oel, das nicht weiter gereinigt wird. Die Ergebnisse sind in Tabelle 1 zusammengefasst.

Using the method according to Example 1 while maintaining the stoichiometry of ethyl chloroacetate by the chlorine compounds given in Table 1 (Examples 2-4) or compound A by the compound of the formula

replaced. The compound of Example 3 is an oil that is not further purified. The results are summarized in Table 1.

Example 6:

A suspension of 36 parts of sodium in 200 parts of toluene is at 0 _° C with a solution of 30 parts of 8,9-dithia-bicyclo [4.3.0] -Δ ^1,6- non-7-thione of the formula (A) and 12 parts of CS ₂ in 220 parts of toluene. The mixture is left to stand at 20 _° C. for 3 hours. Then 220 parts of water are added. The aqueous phase is separated off and acidified with the exclusion of atmospheric oxygen with 180 parts of 10% sulfuric acid. The precipitate is filtered off, washed with ice-cold water, a little ice-cold methanol and cyclohexane and dried in the dark under high vacuum. 31.5 parts of the garnet-red product of the formula (C) are obtained, which can be converted into bismethylated derivative (D) (mp. 148 _° C.) with dimethyl sulfate in 67% yield:

Example 7:

welches nach zusätzlicher Reinigung bei 134-135,5_°C schmilzt.5 parts of the product (C) from Example 6 are dissolved in 39 parts of 1N sodium hydroxide solution and mixed with 3 parts of 2-chloroethanol at room temperature. After a few minutes, the product precipitates under the influence of heat. The reaction mixture is stirred for a further 2 hours, then suction filtered and washed with water. The moist crude product is heated to reflux with 150 parts of methanol for 30 minutes, then suctioned off cold. 6 parts of a red-orange product of the formula (E) are obtained

which melts at 134-135.5 _° C after additional cleaning.

Example 8:

The product of Example 7 is esterified in toluene with 2-ethyl-hexanoyl chloride and triethylamine by conventional methods. A dark red oil of the formula (F) is obtained:

Example 9:

welches bei 105,5-106,5_°C schmilzt.Using the method according to Example 7, chloroethanol is replaced by 1- (2-chloroethyl) pyrrolidine while maintaining the stoichiometry. The product of the formula (G) is obtained

which melts at 105.5-106.5 _° C.

Example 10:

welches bei 72,4-74°C schmilzt.Using the method according to Example 7, chloroethanol is replaced by 2-chloroethyl ethyl ether while maintaining the stoichiometry. The red product of the formula (H) is obtained

which melts at 72.4-74 ° C.

B) Application examples: Example 11:

• 1. W.L. = Weld load (Schweisslast). Das ist die Last, bei der die-4 Kugeln innerhalb von 10 Sekunden zusammenschweissen.
• 2. W.S.D. = Wear Scar Diameter in mm: Das ist der mittlere Verschleissdurchmesser bei einer Belastung von 40 kg während 10 bzw. 30 Minuten.

With the Shell four-ball apparatus (IP 239/73) Extreme pressure and wear lubricant test for oils and greases four ballmachine, ASTM D 2783-81) the following values are determined:

• 1. WL = Weld load. This is the load that the 4 balls weld together within 10 seconds.
• 2. WSD = Wear Scar Diameter in mm: This is the average wear diameter with a load of 40 kg for 10 or 30 minutes.

A base oil from Shell (Catenex P 941®) and water containing 0.5% by weight of potassium hydroxide solution, 1.5% by weight of triethanolamine and 0.75% by weight of corrosion inhibitor are used as test liquids for the effectiveness of the additives. contains inhibitor (Reocor 184®, Ciba-Geigy). The pH of this solution together with the additive is 8.5. The results are shown in Table 2. In addition, the evaluation of copper corrosion according to ASTM D-130 is given.

Example 12:

With the friction wear scales according to Reichert (Reichert Wear Test DBGM 1749247) the Ver wear cap determined (Kadmer et al., Mineralöltechnik 1958 (2), 1-17).

In this friction tester, a firmly clamped test roller is pressed onto a rotating slip ring with a lower lever system. Dip a third in the liquid to be tested, the pressure absorption capacity of which is to be assessed. When the slip ring is not running, depending on the pressure absorption capacity of the liquid on the test roller, there are abraded surfaces (wear spheres), the size of which depends on the load-bearing capacity of the test substance.

Test conditions of the device:

Water, which contains 0.75% by weight of corrosion inhibitor (Reocor 184 @), 0.5% by weight of potassium hydroxide solution, 1.5% by weight of triethanolamine and 2.5% by weight, is used as the test liquid for the effectiveness of the additives. Contains additive (pH 8.5). The result is shown in Table 3.

Before and after the actual measurement run, control measurements are carried out with a mixture of 50% by weight of water and 50% by weight of ethanol, wear values around 40 mm ^{2 being} observed.

Example 13:

With the cam follower device, the load behavior is examined according to "Tribology and Lubrication Technology" 31/3, p. 164 (1984). In a modification of this description, one hour at 1000 N, 1100 N, 1200 N etc. up to a maximum of 2000 N or until significant wear occurs. The measure is the damage burden.

An oil of specification SAE 10W-30 is used as the test liquid for the effectiveness of the additives. It consists of a mixture of 72.8 wt% mineral oil (ISO VG 32), 11.2 wt% XOA 938 _@ (Orogil) and 6 wt% Viscoplex 610 _@ (Roehm). The results are summarized in Table 4 below.

Example 14:

With the help of the method developed by C.S. Ku and S.M. Hsu in Lubrication Engineering Vol. 40 (2), 75-83 [1984] (Thin-film Oxygen Uptake Test, "TFOUT") i, it is determined how long an additive is able to protect lubricants from metal ions to preserve catalyzed oxidative degradation. The values given are mean values of two independent test runs. A typical motor oil (composition: mineral oil 82.05% (ISO-VG32); detergent / dispersant 11.2%; VI improver 6.0%; ZnDDP 0.75%) is used as the test liquid, but this is only half of the usually contains added zinc dialkyldithiophosphates. The results are shown in Table 5.

Claims (19)

1. A composition containing a lubricant or a hydraulic fluid and at least one compound of the formula I

in which both R¹, independently of one another, are a hydrogen atom, a metal cation, NH₄⊕, primary, secondary, tertiary or quaternary ammonium, linear or branched C₁-C₂₄alkyl, unsubstituted or C₁-C₁₈alkyl-substituted cycloalkyl or cycloalkylalkyl having 3 to 7 ring C atoms, C₇-C₁₆aralkyl or C₈-C₄₀alkaralkyl, where C₁-C₂₄alkyl is unsubstituted or may be substituted by -NR4R5, -NR4R5R6, - OR⁷, -SR⁷, -(C_mH_2mO)_nR⁸, -C(O)OR⁹ or C₁-C₂₀acyloxy, in which R⁴, R⁵ and R⁶, independently of one another, are a hydrogen atom or unsubstituted or -OH-substituted C₁-C₂₀alkyl, or R⁴ and R⁵ together are tetramethylene, pentamethylene or 3-oxapentylene, R⁷ is a hydrogen atom, linear or branched C₁-C₁₈alkyl, unsubstituted or C₁-C₁₂alkyl-substituted cyclohexyl, phenyl or benzyl, R8 is a hydrogen atom, C₁-C₁₈alkyl or C₁-C₂₀acyl, and R⁹ is a hydrogen atom, the radical, reduced by one hydroxyl group, of a monohydric alcohol, a metal cation, NH₄⊕, or primary, secondary, tertiary or quaternary ammonium, m is an integer from 1 to 6, and n is a number from 1 to 20, R² and R³, independently of one another, are a hydrogen atom or linear or branched C₁-C₂₀alkyl, or R₂ and R₃ together are -CpH₂p- in which p is an integer from 2 to 9.

2. A composition according to claim 1 wherein, in formula I, both Rⁱ, independently of one another, are a hydrogen atom, an alkali metalcation, an alkaline-earth metal cation or a transition metal cation, NH₄⊕, primary, secondary, tertiary or quarternary ammonium having C₁-C₁₈alkyl groups, linear or branched C₁-C₁₂alkyl, unsubstituted or C₁-C₆alkylsubstituted cyclohexyl, C7-Ct2phenylalkyl or C₈- ₃₀alkylbenzyl, where the C₁-C₁₂alkyl may be substituted by -NR4RS or, NR4R5R6, -OR7, -SR7, - (C_mH_2m)_n-R⁸, -C(O)OR⁹ or C₁-C₁₂acyloxy, in which R⁴, R⁵, and R⁶, independently of one another, are a hydrogen atom or C₁-C₁₈alkyl, R⁷ is a hydrogen atom, linear or branched C₁-C₁₂alkyl, unsubstituted or C₁-C₁₂alkyl-substituted phenyl or benzyl, R⁸ is a hydrogen atom, C₁-C₁₂alkyl or C₁-C₁₂acyl, and R⁹ is a hydrogen atom, the radical, reduced by one hydroxyl group, of a monohydric alcohol having 1 to 20 C atoms or linear or branched C₁-C₂₀alkyl, m is an integer from 1 to 4, and n is an number from 1 to 6, R² and R₃, independently of one another, are a hydrogen atom or linear or branched C₁-C₁₂alkyl, or R² and R3 together are -CpH₂p- in which p is an integer from 2 to 7.

3. A composition according to claim 1, wherein both R¹ in formula I are H, NH^4⊕, Li^⊕, Na^⊕, K^⊕, Mg2₊, Ca2+ Cu^⊕ or Zn2+.

4. A composition according to claim 1, wherein both ammonium R¹ in formula I have the formulae R¹⁰NH₃, R¹⁰R¹¹NH₂, R¹⁰R¹¹R¹²NH oder R¹⁰R¹¹R¹²R¹³N^⊕ in which R¹⁰, R¹¹, R¹² and R¹³, independently of one another, are unsubstituted or hydroxyl-substituted, linear or branched C₁-C₁₈alkyl.

5. A composition according to claim 4, wherein R¹⁰ is linear or branched C₆-C₁₈alkyl, and R¹¹, R¹² and R¹³ are linear or branched C₁-C₄alkyl.

6. A composition according to claim 1, wherein R4, R5 and R⁶, independently of one another, are a hydrogen atom or unsubstituted or -OH-substituted C₁-C₁₂alkyl.

7. A composition according to claim 1, wherein both R¹ in the formula I are linear or branched C₂-C₁₈alkyl.

8. A composition according to claim 1, wherein both R¹ in the formula I are -C(O)OR⁹-substituted C₁-C₆alkyl, and R⁸ is as defined in claim 1.

9. A composition according to claim 8, wherein both R¹ correspond to the radical of the formula - CH₂C(O)OR9 in which R9 is H, NH₄⊕, a metal cation, primary, secondary, tertiary or quaternary ammonium or C₁-C₂₀alkyl.

10. A composition according to claim 1, wherein R² and R³ are a hydrogen atom or C₁-C₄alkyl, or R² and R³ together are the -CpH₂p- group in which p is an integer from 2 to 5, preferably 2 or 3.

11. A composition according to claim 1, wherein the compound of the formula I is present in an amount from 0.01 to 10% by weight, relative to the lubricant or the hydraulic fluid.

12. A composition according to claim 1, which additionally contains 0.01 to 15% by weight, relative to the lubricant or the hydraulic fluid, of a zinc dialkyldithiophosphate.

13. A compound of the formula la

in which both R¹, independently of one another, are a hydrogen atom, a metal cation, NH₄⊕, primary, secondary, tertiary or quaternary ammonium, unsubstituted or C₁-C₁₈alkyl-substituted cycloalkyl or cycloalkylalkyl having 3 to 7 ring C atoms, C₇-C₁₆aralkyl or C₈-C₄₀alkaralkyl, linear or branched C₃-C₂₄alkyl, or C₁-C₂₄ alkyl which is unsubstituted or substituted by -NR4R5, -NR4R5R6, -OR7, -SR7, -(C_mH_2mO)_nR⁸, -C(O)OR⁹ or C₁-C₂₀acyloxy, in which R⁴, R⁵ and R⁶, independently of one another, are a hydrogen atom or unsubstituted or -OH-substituted C₁-C₂₀alkyl, or R⁴ and R⁵ together are tetramethylene, pentamethylene or 3-oxapentylene, R7 is a hydrogen atom, linear or branched C₁-C₁₈alkyl, or unsubstituted or C₁-C₁₂alkyl-substituted cyclohexyl, phenyl or benzyl, R⁸ is a hydrogen atom, C₁-C₁₈alkyl or C₁-C₂₀acyl, and R⁹ is a hydrogen atom, the radical, reduced by one hydroxyl group, of a monohydric alcohol, a metal cation, NH₄⊕, or primary, secondary, tertiary or quaternary ammonium, m is an integer from 1 to 6, and n is a number from 1 to 20, R² and R³, independently of one another, are a hydrogen atom or linear or branched C₁-C₂₀alkyl, or R₂ and R₃ together are -CpH₂p- in which p is an integer from 2 to 9.

14. A compound according to claim 13, in which both R¹ in formula la are C₆-C₁₈alkyl.

15. A compound according to claim 13, in which both R¹ in formula la are -C(O)OR9-substituted C₁-C₆alkyl in which R^s has the meaning specified in claim 13.

16. A compound according to claim 15, in which both R¹ correspond to the radical of the formula -CH₂C(O)OR⁹ in which R⁹ is H, NH₄⊕, a metal cation, primary, secondary, tertiary or quaternary ammonium or C₁-C₂₀alkyl.

17. A compound according to claim 13, in which, in formula la, R² and R³, independently of one another, are a hydrogen atom or C₁-C₄alkyl, or R² and R³ together are -CpH₂p- in which p is an integer from 2 to 5 and preferably 2 or 3.

18. The use of a compound of the formula I according to claim 1 as an additive in lubricants or hydraulic fluids.

19. The use of a compound of the formula la according to claim 13 as an additive in lubricants or hydraulic fluids.