MXPA98006334A - Heterociclic tioeteres as additives for lubrican - Google Patents

Abstract

This invention relates to compounds which are suitable as ash-free anti-wear additives, and antioxidants, to lubricating compositions containing said compounds as well as to their use. Particularly preferred are compounds of formula. (See Formula) In the preferred compounds I ', R 2 is isooctyloxycarbonylmethyl, r 3 is isoctyloxycarbonylmethythiomethyl, and R 4 is hydrogen, R 2 is tert-nonyl, R 3 is tert-nonyl thiomethyl and R 4 is hydrogen, R 2 is isooctyloxycarbonylmethyl, R 3 is hydrogen and R 4 is isooctyloxycarbonylmethythiomethyl; tert-nonyl, R3 is hydrogen and R4 is tert-nonyl-thiomethyl. In the preferred compounds II ', R2 and R'2 are isooctyloxycarbonylmethyl, R3 and R'3 are isooctyloxycarbonylmethythiomethyl and R4 and R4 are hydrogen; or R2 and R'2 are tert-nonyl, R3 and R3 are tert-nonylthiomethyl and R 4 and R 4 are hydrogen, R 2 and R 2 are isooctyloxycarbonylmethyl, R 3 and R 3 are hydrogen and R 4 and R 4 are isooctyloxycarbonylmethylthio, R 2 and R 2 are tert-nonyl, R 3 and R 3 are hydrogen. and R4 and R4'are tert-nonylthiomethyl

Description

"HETEROCICLIC TIOETHES AS ADDITIVES FOR LUBRICANTS" Heterocyclic thioethers as additives for lubricants The present invention relates to compounds of formulas I and II, which are suitable as anti-wear additives and ash-free antioxidants, to lubricant compositions containing compounds of the formulas I and II, as well as to their use. For the operation of combustion engines, it is necessary to use lubricants that have a low metal content and, therefore, a low ash content, and also, in view of compatibility with the exhaust gas catalyst , a low phosphorus content. The purpose of this invention is therefore to provide additives free of metal or phosphorus-free additives or combinations of additives, with an action similar to the good antioxidant protection and wear of the zinc dialkyldithiophosphates used to date. The specification of US Patent 3,591,475 describes the preparation of asymmetric dithioethers of general formula by addition of a mercaptan R'SH to an allyl sulfide (RS-CH2CH = CH2). The definitions of R and R 'include a large number of substituents of different structures. There is no given description of a dithioether containing a heterocyclic radical as a single defined compound. Benzothiazolyl is mentioned only as an example in the sense of an enumeration. The use of the compounds described in the specification of the US 3 patent. 591 .475 is also described without any specificity. Its possible application as an agrochemical product with antiparasitic properties is mentioned. It is further indicated that these compounds are suitable as stabilizers for polyolefins and also as additives for lubricants. The preparation of benzothiazolyl dithioethers of formula (R = Et, tert-but, phenyl, Et2OH, acetyl), with herbicidal activity, is described on page 1847 of the English translation of Syntheses on the Basis of 2-benzothiazolylvinyl Sulfide, Zhurnal Organicheskoi Khi ii, vol 2, n "10, pp. 1883 -1891, October 1966. The specification of US Patent 5,258,258 discloses processing solutions for the development of lithographic printing plates, containing thiadiazolyl dithioethers of formula (n1 (n2 = 0-2; R1 (R2 = alkylene of 1 to 5 carbon atoms) The specification of US Pat. No. 5,051,198 describes the reaction products obtainable by reacting the mercaptans with the ß These reaction products can be used as antioxidants The present invention relates to compounds of formulas I and II described above, which are suitable as improved anti-wear additives, free from ash and phosphorus, and which additionally possess an anti-oxidant effect. -oxidant: wherein Ri is hydrogen or alkyl of 1 to 20 carbon atoms; R 2 is a substituent of the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, bicycloalkyl of 7 to 12 carbon atoms, phenyl, alkylphenyl of 7 to 18 carbon atoms, naphthyl and phenylalkyl of 7 to 9 carbon atoms, which substituent can be substituted with one or more substituents of the group consisting of amino, carboxyl and hydroxyl and / or can be interrupted by one or more bivalent radicals from the group consisting of -0-, -NR6- , -C (= 0) -0-, -0-C (= 0) -, -C (= 0) -NRs-, and -NR6-C (= 0) -; R3 and R4 are hydrogen or have the meanings of R2, with the proviso that R2 is alkyl of 4 to 20 carbon atoms if R3 and R are hydrogen. R5 is hydrogen or partial formula groups: wherein R2, R3 and R4 have the meanings cited or have the meaning of R2, and R-s is hydrogen or alkyl of 1 to 4 carbon atoms. The compounds of formula I and II are particularly suitable as multifunctional anti-wear additives with an additional antioxidant effect for lubricants, gear oils, hydraulic fluids and for the machining of metals as well as for greases. They are oils substantially free of ash and phosphorus. The definitions and terms employed in the scope of the description of this invention, preferably have the following meanings: Examples of alkyl of 1 to 20 carbon atoms are methyl, ethyl, n- or isopropyl or n-, sec- or tert. -butyl and also pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl straight or branched chain, mainly isooctyl or tert-nonyl. Examples of cycloalkyl of 5 to 12 carbon atoms are cyclopentyl or cyclohexyl. Examples of bicycloalkyl of 7 to 12 carbon atoms are p. ex. bornyl or norbornyl. Examples of alkylphenyl of 7 to 18 carbon atoms are phenyl which is substituted with mono-, di- or trimethyl. Examples of phenylalkyl of 7 to 9 carbon atoms are p. ex. benzyl or 2-phenylethyl. In another of its aspects, this invention also relates to compounds of formula I and II including all cases of isomerism, for example binding isomers or este-reisomers, which result in the presence of a chiral center. These cases of isomerism include optically pure enantiomers, diastereomers, as well as racemic mixtures. Preferred compounds are those of formula I and II described above, wherein Rj. it's hydrogen; R2 is a substituent of the group consisting of alkyl of 1 to 20 carbon atoms, phenyl, alkylphenyl of 7 to 18 carbon atoms and phenylalkyl of 7 to 9 carbon atoms, which substituent can be substituted with one or more substituents of the group formed by amino, carboxyl and hydroxyl and / or may be interrupted with one or more bivalent radicals from the group consisting of -O-, -NRS-, -C (= 0) -0-, -0-C (= 0) - . -C (= 0) -NR6 and -NRß-C (= 0) -; R3 and R4 are hydrogen or have the meaning of R2 with the proviso that R2 is alkyl of 4 to 20 carbon atoms if R3 and R4 are hydrogen; Rs has the meanings of R2 or is a group of partial formula (A) and (B), in which R2, R3 and R4 have the meanings cited, - and Rβ is hydrogen or alkyl. Particularly preferred are compounds of formula I and II in which R x is hydrogen; R 2 is a substituent of the group consisting of alkyl of 1 to 20 carbon atoms, phenyl, alkylphenyl of 7 to 18 carbon atoms and phenylalkyl of 7 to 9 carbon atoms, which substituent can be interrupted with one or more bivalent radicals of the group formed by -0-, -C (= 0) -0- and -0-C (= 0) -; R3 and R4 are hydrogen or have the meanings of R2 with the proviso that R2 is alkyl of 4 to 20 carbon atoms if R3 and R4 are hydrogen; Rs has the meanings of R2 or is a group of partial formula (A) and (B), in which R2, R3 and R4 have the meanings cited. Particularly preferred of this invention are the compounds of formula I and II, wherein R x is hydrogen; R2 is alkyl of 1 to 20 carbon atoms which may be interrupted with a bivalent radical of the group consisting of -0-, -C (= 0) -0- and -0-C (= 0) -; R3 and R4 are hydrogen or have the meanings of R2, with the proviso that R2 is alkyl of 4 to 20 carbon atoms if R3 and R4 are hydrogen; R5 has the meanings of R2 or is a group of partial formula (A) and (B), in which R2, R3 and R4 have the meanings cited. Particularly preferred are the compounds of formula wherein R is alkoxycarbonylmethyl of 4 to 18 carbon atoms, R3 is alkoxycarbonylmethythiomethyl of 4 to 18 carbon atoms and R4 is hydrogen; or R2 is alkyl of 5 to 12 carbon atoms, R3 is alkylthiomethyl of 5 to 12 carbon atoms, and R4 is hydrogen, - or R2 is alkoxycarbonylmethyl of 4 to 18 carbon atoms, R3 is hydrogen and R4 is alkoxycarbonylmethythiomethyl; or R2 is alkyl of 5 to 12 carbon atoms, R3 is hydrogen and R4 is alkylthiomethyl of 5 to 12 carbon atoms, and compounds of formula: wherein R2 and R'2 are alkoxycarbonylmethyl of 4 to 18 carbon atoms, R3 and R'3 are alkoxycarbonylmethythiomethyl of 4 to 18 carbon atoms, and R4 and R'4 are hydrogen; or R 2 and R 2 are alkyl of 5 to 12 carbon atoms, R 3 and R 3 are alkylthiomethyl of 5 to 12 carbon atoms, and R 4 and R 4 are hydrogen, or R 2 and R 2 are alkoxycarbonylmethyl of 4; to 18 carbon atoms, R3 and R'3 hydrogen, and R4 and R'4 are alkoxycarbonylmethythiomethyl of 4 to 18 carbon atoms or R2 and R'2 are alkyl of 5 to 12 carbon atoms, R3 and R3 are hydrogen and R 4 and R 4 are alkylthiomethyl of 5 to 12 carbon atoms. Especially preferred are compounds of formula-R, wherein R 2 is isooctyloxycarbonylmethyl, R 3 is iso-octyloxycarbonylmethythiomethyl, and R 4 is hydrogen; or R 2 is tert-nonyl, R 3 is tert-nonyl thiomethyl and R 4 is hydrogen; or R 2 is isooctyloxycarbonylmethyl, R 3 is hydrogen and R 4 is isooctyloxycarbonylmethythiomethyl, - or R 2 is tert-nonyl, R 3 is hydrogen and R 4 is tert-nonyl thiomethyl, and also compounds of formula II ', wherein R 2 and R 2 are isooctyloxycarbonylmethyl, R 3 and R'3 are isooctyloxycarbonylmethythiomethyl and R4 and R'4 are hydrogen; or R2 and R'2 are tert-nonyl, R3 and R'3 are tert-nonylthiomethyl and R4 and R'4 are hydrogen; or R2 R'j are isooctyloxycarbonylmethyl of 5 to 10 carbon atoms, R3 and R'3 are hydrogen and R4 and R'4 are isooctyloxycarbonylmethyl; or R2 and R'2 are tert-nonyl of 5 to 10 carbon atoms, R3 and R3 are hydrogen and R4 and R4 are tert-nonylthiomethyl. The invention further relates to compositions with lubricants containing a compound of formula I or II or mixtures thereof in combination with a base oil of a viscosity suitable for lubrication, or with fuels. This invention also relates to a method for improving the performance of lubricants or lubricating greases, such as engine oil, turbine oil, gear oil, hydraulic fluid or fluid for machining metals or liquid fuels, e.g. ex. diesel fuels or fuels comprising the addition of at least one compound of formula I or II to achieve a reduction in friction and / or an antioxidant effect. Accordingly, this invention also relates to the use of compounds of formula I or II as additives in lubricants or lubricating greases, such as motor oils, turbine oils, gear oils, hydraulic fluids, fluids for metal machining, lubricating greases or fuels for diesel or fuels. A base oil of viscosity suitable for lubrication, for the preparation of lubricating greases or lubricating fluids, for machining metals, for gears or for hydraulic fluids can be used. Said lubricating greases or lubricating fluids, for machining metals, for gears or hydraulic fluids, are based for example on lubricants or mineral or synthetic oils, or mixtures thereof. Those skilled in the art are familiar with them, and are described in the corresponding literature, for example, in Chemistry and Technology of Lubricant; Mor tier, R .M. and Orszulik, S. T. (Editors); 1992 Blackie and Son Ltd. for GB, VCH -Publishers N. Y. for U. S., ISBN 0-216-92921 -0, see pages 208 et seq., And 269 et seq .; in Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition 1969, J. Wiley and sons, New York, vol. 13, page 533 et seq. (Hydraulic Fluids) / Performance Testing of Hydraulic Fluids; R. Tourret and E. P. Wright, Hyden and Son Ltd. GB, on behalf of The Insti tute of Petroleum London, ISBN 0 85501 317 6; Ullmann 's Encyclopedia of Ind. Chem., 5th edition completely revised, Verlag Chemie, DE - Weinhei, VCH - Sublishers for US, vol A 15, page 423 et seq. (Lubricant), vol A 13, page 165 et seq. hydraulic fluids). The lubricants are preferably oils and fats, based on p. ex. in a mineral oil. The oils are the preferred ones. Another group of lubricants that can be used are vegetable or animal oils, fats, tallow and waxes, or their mixtures with each other, or their mixtures with the mentioned mineral or synthetic oils. Vegetable and animal oils, fats, tallow and waxes are, for example, palm kernel oil, palm oil, olive oil, beet oil, rape seed oil, linseed oil, peanut oil, oil soybean, cottonseed oil, sunflower oil, pumpkin seed oil, coconut oil, corn oil, castor oil, walnut oil and mixtures thereof, fish oils, slaughterhouse animal tallow, such such as beef tallow, legged oil vaccines and bone sebum, as well as their epoxidized and sulfoxidated modified forms, for example epoxidized soybean oil. Examples of synthetic lubricants include lubricants based on aliphatic or aromatic carboxylates, polymeric esters, polyalkylene oxides, phosphates, poly-α-olefins or silicones, on a divalent acid diester with a monovalent alcohol, e.g. ex. dioctyl sebacate or dinonyl adipate, in a triester of trimethylolpropane with a monovalent acid or with a mixture of said acids, e.g. ex. , trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, in a tetraester of pentaerythritol with a monovalent acid or with a mixture of said acids, e.g. ex. pentaerythritol tetracaprylate, or in a complex ester of monovalent and divalent acids with polyhydric alcohols, for example a complex ester of trimethylolpropane with caprylic acid and sebacic acid or a mixture thereof. They are particularly suitable, in addition to mineral oils, e.g. ex. poly-a-olefins, lubricants based on esters, phosphates, glycols, polyglycols and polyalkylene glycols and their mixtures with water. Fluids for the machining of metals and hydraulic fluids can be prepared based on the same substances described above for lubricants. These are often emulsions of these substances with water or other liquids.

The lubricant compositions of this invention are used, for example, in combustion engines, e.g. ex. in equipped motor vehicles p. ex. with Otto, Diesel engines, two-stroke engines, Wankel or the orbital type. The compounds of formula I or II are easily soluble in lubricants, in fluids for metalworking and in hydraulic fluids, and are therefore particularly suitable as additives for lubricants, for metalworking and for hydraulic fluids, The compositions conveniently contain from 0.005 to 10.0% by weight of the compounds of formula I or II, preferably 0.01-5.0% by weight, and more preferably 0.01-0.9% by weight .

The compounds of formula I or II can be mixed with the lubricants in a manner known per se. The compounds are easily soluble, for example in oleophilic solvents, e.g. ex. in oils. They can also be used in conjunction with additional additives to prepare a concentrate or a so-called "additive packet", which depending on the consumption can be diluted with the lubricant corresponding to the concentrations to be used. Lubricants, fluids for the machining of metals and hydraulic fluids, can additionally contain other additives that can be added to further improve their basic properties. These additives include: additional antioxidants, metal passivators, oxidation inhibitors, viscosity index improvers, freezing point depressants, dispersants, detergents, other additives for extreme pressures, antiwear and friction-reducing additives. When appropriate, these additives can act synergistically with each other or with the new compounds. Said additives are added in the usual amounts ranging from about 0.01 to 10.0% by weight each. If it is still necessary to add additives containing phosphorus or a metal, it is then preferable that these additives are added in small amounts, for example about 0.01 to 0.5% by weight.

Examples of other additives are: Examples of phenolic antioxidants: l.l. Alkylated monophenols, for example, 2,6-di-tert-butyl-4-methylphenol, 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-isobutyl-enol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethyl enol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1 '-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1' - il) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof. 1.2. Alkyltiomethyl-enols. for example 2,4-dioctyl-thiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol. 1.3. Hydroquinones and alkylated hydroquinones, for example 2, 6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4 -octade-cycloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di stearate -tert-butyl-4-hydroxyphenyl, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) adipate. 1.4. Tocopherols, a-, β-, and-, d-tocopherol and mixtures thereof (vitamin E). 1.5. Hydroxylated thiodiphenylethers. for example, 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiobis- (4-octylpheno-nol), 4,4'-thiobis- (6-tert-butyl) 3-methylphenol), 4,4'-thiobis- (6-tert-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di-sec-amylfe-nol), 4,4 ' bis (2,6-dimethyl-4-hydroxyphenyl) disulfide. 1.6. Alkylidenebisphenols. for example, 2,2 '-methylene-bis- (β-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4] -methyl-6- (a-methyl-clohexyl) -phenol], 2,2 '-methylenebis (4-methyl-6-cyclohexyl-phenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butyl) butylphenol), 2,2 '-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidebis (6-tert-butyl-4-isobuylphenol), 2,2'-methylenebis [6-) (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol) , 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phenylbutane, 2,6-bis- (3 - tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 1,1-bis- (5-tert-butyl-4-hydroxy-2-methyl-phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis- [3, 3-bis- (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis- (3-tert.butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert- butyl-4-methyl-phenyl] terephthalate, 1,1-bis- (3, 5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis- (3,5-di-t) erc-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n -dodecylmercaptobutane, 1, 1, 5, 5-tetra- (5) -tert-butyl-4-hydroxy-xi-2-methylphenyl) pentane. 1.7. O-, N- and S-benzyl compounds. for example 3, 5, 3 ', 5' -tetra-tert-butyl-4,4 '-dihydroxydibenzylether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert. -butylbenzylmercaptoacetate, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di) -tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-buyl-4-hydroxybenzylmercaptoacetate. 1.8. Hydroxybenzylated malonates. for example diocta-decyl-2, 2-bis- (3, 5-di-tert-butyl-2-hydroxybenzyl) -malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) ) -malonate, didodecylmercaptoethyl-2, 2-bis- (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1, 1,3,3-tetramethylbutyl) phenyl] -2, 2 bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate. 1.9. Aromatic hydroxybenzyl compounds. for example 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl) -4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol. 1.10. Triazine compounds. for example 2, 4-bis (octyl-mercapto) -6- (3, 5 -ditere-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1 , 3, 5-triazine, 2,4,6-tris (3,5-di-tere-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5- di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3, 5) di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5- triazine, 1,3, 5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate. l.ll. Benzylphosphonates for example dimethyl-2, 5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hi- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester. 1.12. Acylaminophenols for example, 4-hydroxylauranyl-da, 4-hydroxystearanilide, N- (3, 5-di-tert-butyl-4-hydroxy-phenyl) -carbamic acid. 1.13. Esters of ß- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid with monovalent or polyvalent alcohols, p. ex. : methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propane-diol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) ) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6,7-trioxabicyclo [2.2.2] octane. 1.14. Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with monovalent or polyvalent alcohols, p. ex. : with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris ( hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo [2. 2. 2] -octane. 1.15. Esters of ß- (3,5-dicyclohexyl-4-hydroxy-phenyl) -propionic acid with monovalent or polyvalent alcohols, p. ex. : methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-bis (hydroxy-yl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6,7-trioxabicyclo [2.2.2] octane. 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with monovalent or polyvalent alcohols, p. ex. : methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo [2.2.2] octane. 1.17. Amides of ß- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid. p. ex. : N, N'-bis (3,5-di-tert-butyl-4-hi-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N , N'-bis (3,5-di-tere-butyl-4-hydroxyphenylpropionyl) -hydrazine. 1.18. Ascorbic acid (vitamin C) 1.19. Amine antioxidants, for example N, N'-di-iso-propyl-p-phenylenediamine, N, N '-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) - p-Phenylenediamine, N, N'-bis (l-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N '-dicyclohexyl-p-phenylenediamine , N, N'-di-phenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N '-phenyl-p-phenylenediamine, N- (1, 3- dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-to -sulfunsulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopro-poxydiphenylamine, N-phenyl-1-naphthylamine, N- ( 4-tert-octylfe-nyl) -l-naphthylamine, N-phenyl-2-naphthylamine, oc-tilated diphenylamine, for example, p, p '-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxy-phenyl) amine, 2, 6 di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [( 2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3' -dimethylbutyl) phenyl] amine, N-phenyl-1-naphthylamine tert. -octylated, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenyl-amines, a mixture of mono- and dialkylated nonildiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines; a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3, 3-dimethyl-4H-1, 4-benzo-thiazine, phenothiazine, a mixture of tert-butyl / tert-octyl-phenothiazines mono- and dialkylated, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-l, 4-diaminobut-2-ene, N, N-bis (2,2,6, 6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethyl-piperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2, 2,6,6-tetramethylpiperidin-4-ol Examples of other antioxidants: aliphatic or aromatic phosphites, thiodipropionic acid or thiodiacetic acid esters, or dithiocarbamic or dithiophosphoric acid salts, 2, 2, 12, 12 -tetramethyl-5 , 9-dihydroxy-3,7, 1-trithiatridecane and 2, 2, 15, 15-tetramethyl-5, 12-dihydroxy-3, 7, 10, 14-tetrathiahexadecane Examples of metal deactivators, eg for copper , are: a) Benzotriazoles and derivatives thereof, for example 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriaz ol, 4-or 5-alkylbenzotriazoles (p. ex. tolutriazole) and the derivatives thereof, 4, 5, 6, 7-tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole; Mannich bases of benzotriazole or tolutriazole, p. ex. 1- [bis (2-ethylhexyl) aminomethyl) tolutriazole and 1- [bis (2-ethylhexyl) aminomethyl) benzotriazole; and alkoxyalkylbenzotriazoles such as 1- (nonyloxy-methyl) benzotriazole, 1- (1-butoxyethyl) benzotriazole and 1- (1-cyclohexyloxybutyl) olu-triazole. b) 1, 2, 4-triazoles and derivatives thereof, for example 3-alkyl (or aryl) -1, 2, 4-triazoles, and Mannich bases of 1,2,4-triazoles, such as 1- [bis (2-ethylhexyl) aminomethyl-1,2,4-triazole; alkoxyalkyl-1,2,4-triazoles such as 1- (1-bu-toxiethyl) -1,2,4-triazole; and acylated 3-amino-1,2,4-triazoles. c) Derivatives of imidazole, for example 4,4'-methylenebis (2-undecyl-5-methylimidazole) and bis [(N-methyl) imidazol-2-yl] carbinol octyl ether. d) Heterocyclic sulfur-containing compounds, for example 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4 thiadiazole and derivatives thereof; and 3, 5-bis [di (2-ethylhexyl) aminomethyl] -l, 3, -thiadiazolin-2-one. e) Amine compounds, for example salicylicidene-propylenediamine, salicylaminoguanidine and salts thereof. Examples of oxidation inhibitors are: a) Organic acids, their esters, metal salts, amine salts and anhydrides, for example alkyl- and alkenyl-succinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl- and alkenyl succinic acids, 4-nonylphenoxy acetic acid, alkoxy- and alkoxyethoxycarboxylic acids such as dodecyloxyacetic acid, dodecyloxy (ethoxy) acetic acid and the amine salts thereof, and also N-oleoylsarcosine, sorbitan monooleate, lead naphthenate, alkenyl succinic anhydrides, for example dodecenylsuccinic anhydride, 2- (2-carboxyethyl) -l-dodecyl-3-methylglycerol and the salts thereof, in particular the sodium salts and the triethanolamine salts. b) Nitrogen-containing compounds, for example: i. Primary, secondary or tertiary, aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil soluble alkyl ammonium carboxylates, and also 1- [N, N-bis (2-hydroxyethyl) amino] -3- (4-nonylphenoxy) propan-2-ol. ii. Heterocyclic compounds, for example: imidazolines and substituted oxazolines, and 2-heptadecenyl-1- (2-hydroxyethyl) imidazoline. c) Phosphorus-containing compounds, for example: amine salts of partial esters of phosphoric acid or partial esters of phosphonic acid, and zinc dialkyldithiophosphates. d) Sulfur-containing compounds, for example: barium dino-n-naphthalene sulphonates, petroleum calcium sulfonates, alkyl-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids and salts thereof. e) Glycerin derivatives, for example glycerin monooleate, 1- (alkylphenoxy) -3- (2-hydroxyethyl) glycerin, 1- (alkylphenoxy) -3- (2,3-dihydroxypropyl) glycerin and 2-carboxyalkyl-1,3-dialkylglycerin. Examples of viscosity index improvers are: Polyacrylates, polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers and polyethers. Examples of freezing point depressants are: Poly (meta) acrylates, ethylene / vinyl acetate copolymer, alkyl polystyrenes, fumarate copolymers, alkylated naphthalene derivatives. Examples of dispersants / surfactants are: Polybutenyl succinate amides or imides, polybutenylphosphonic acid derivatives and basic magnesium, calcium and barium sulfonates and basic magnesium, calcium and barium phenolates. Examples of additives for extreme pressures and anti-wear are: Compounds containing sulfur and / or phosphorus and / or halogen, for example chlorinated paraffins, sulfurized olefins or vegetable oils (soybean oil and rapeseed oil), alkyl- or aryl- di- or -trisulfides, zinc dialkyldithiophosphates such as zinc bis (2-ethylhexyl) dithiophosphate, zinc dithiocarbamates, such as zinc diamyldithiocarbamate, molybdenum phosphorodithioates, molybdenum dithiocarbamates, triaryl phosphates such as tritolylphosphate, tricresylphosphate, isopropyl phenylphosphate Fate, amine salts of mono- or dialkylphosphoric acids, e.g. ex. mono / di-hexyl phosphate amine salts, amine salts of alkyl phosphonic acids, such as the amine salt of methylphosphonic acid, triaryl phosphites, p. ex. tris [nonylphenyl] phosphite, dialkylphosphites, such as dioctyl phosphite, triaryl monothiophosphates, for example triphenyl thiophosphate or tris- [isononylphenyl] thionophosphate or tert-butylated triphenyl tertiostephosphate, substituted trialkyl mono- or dithiophosphate, for example [(diisopropoxyphosphinothioyl) thio] propionate or bu-tilen-l, 3-bis [(diisobutoxyphosphinothioyl) propionate], trithiophosphates, such as trithiophosphoric acid, S, S, S-tris (isooctyl-2-acetate), amine salts of 3-hydroxy-l, 3-thiaphosphetane-3-oxide, benzotriazoles or derivatives thereof, e.g. ex. bis (2-ethylhexyl) aminomethyl toltriazole, di-thiocarbamates such as methylene-bis-dibutyldithiocarbamate, 2-mercaptobenzothiazole derivatives, p. ex. 1- [N, N-bis (2-ethylhexyl) aminomethyl] -2-mercapto-1H-1,3-benzothiazole, 2,5-dimercapto-1,3,4-thiadiazole derivatives, such as 2, 5 -bis (tert-nonylthio) -1,3,4-thiadiazole. Examples of reducing coefficients of friction are, for example, lard oil, oleic acid, tallow, rapeseed oil, sulfurized fats, amines. Other examples are cited in EP-A-565487.

Examples of special additives for use in acrua / oil fluids for machining metals and hydraulic fluids are: Emulsifiers: petroleum sulfonates, amines such as polyethoxylated fatty amines, nonionic surfactant substances; buffers: alkanolamines; biocides: triazines, thiazolinones, tris-nitromethane, morpholino, pyridine, sodium ethanol; process velocity improvers: calcium sulfonates and barium sulphonates; Examples of fuel additives These additives are described in Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 12, 1994. These are mainly additives for gasoline and diesel. Gasoline: amine antioxidants, in particular para-phenylenediamines, or phenolic antioxidants, p. ex. 2,6-di-tert-butylphenol (as described above), metal deactivators, in particular N, N '-disalicilidene-1,2-propane, benzotriazole, EDTA; oxidation inhibitors, for example, carboxylic acids, sulfonates, amines or amine salts; dispersants, p. ex. esters, high molecular weight amines, Mannich bases, succinimides, borated succinimides, detergents, for example fatty acid amides, nonpolymeric amines, polybute succinimides, polyether amines, low molecular weight amines, sulfonates, salicylic acid derivatives; demulsifiers, for example long-chain alcohols or phenols containing polyethylene or polybutylene groups; anti-knock additives, for example, manganese methylcyclopentadienyltricarbonyl, oxygen compounds, e.g. ex. esters of vegetable oils, ethers, alcohols to improve fuel behavior. Diesel heavy oils: Ignition improvers (cetane index improvers), p. ex. alkyl nitrates, ether nitrates, alkyl diglycol nitrates, organic peroxides; stabilizers, in particular for cracking diesel: amines and other N-containing compounds, which act as radicals interceptors; oxidation inhibitors, as described above; detergents; oxygen compounds as described above, - cold flow improvers, namely for example, freezing point depressants (see above), turbidity point depressants or so-called operability additives (OA), which they are polymeric multi-component systems that improve, among other things, the behavior of the filtering fluidity. Preparation process: The compounds of formula I and II can be obtained in a manner known per se, for example by reaction of a 2-mercaptobenzothiazole of formula with an alcohol or with a functional reagent derived therefrom, or a 2,5-dimercaptothiadiazole of formula with the alcohol of the above formula or with an alcohol Rs-OH or with a functional reagent derived therefrom, with water separation, preferably under acidic conditions. EXAMPLES The invention is illustrated by the following examples. It is understood that the parts or so many percent are by weight, unless otherwise specified. Example 1 . rxr > * -_, S- (E) X - do tectil) a) 156.3 g (0.6 mole) of the product of example 1 b) and 1 ml of concentrated sulfuric acid are added to a suspension consisting of 105.6 g (0.6 mole) of 2-mercaptobenzothiazole in 800 ml of toluene. This mixture is heated to reflux in a water separator for 1 hour. The yellow oil obtained is dissolved in 500 ml of hexane and washed with 50 ml of 2N sodium hydroxide solution and water until neutral (pH 7). The organic phase is concentrated by evaporation and the product is dried under reduced pressure (110 ° C / approx. 0.02 mbars), obtaining 235 g of a pale yellow transparent oil, of medium viscosity (yield, 96% of theory) . nD20: 1.5781; elemental analysis: 64.16% of C (calculated 64.50); 8.62% of H (calculated 8, .61); 4.16% of N (calculated 3.42); approx. 24% of S (calculated 23.48, problematic determination of S). b) The starting material is prepared as follows: IteHMBc-i-ffl + ° l > ^ Na (cat.) * ^^ ecdl.á ^ / 20% c! Ee > oe ?? ° 1 g of sodium (~50 mmol) is added to 140 g (2.4 moles) of propylene oxide. After about 1 hour, 426 g (2 moles) of tert-dodecyl mercaptan are added dropwise at 25-30 ° C (the reaction proceeds exothermically). The mixture is allowed to react for 1 hour at 55-60 ° C and the Sodium is deactivated with approximately 1 ml of acetic acid. The clear pale yellow crude product is fractionated under reduced pressure (106-110 ° C / approx. 0.02 mbars) to obtain 509 g of a transparent colorless oil of medium viscosity (yield, 98% of the theory); nD20: 1.4801. Example 2 Analogously to example la), 16.73 g (0.1 mol) of 2-mercaptobenzothiazole are reacted with 19.03 g (0.1 mol) of 2- (octylthio) ethanol [3547-33-9, Phillips Petroleum , US patent specification 2. 863. 799], obtaining 33 g of a clear colorless oil (yield, 97% of the theory).

Elemental analysis: 60.67% of C (calculated 60.13); 7.40% of H (calculated 7.42); 3.93% of N (calculated 4.12), approx. 27% of S (calculated 28.32, problematic determination of S).

Example 3 I H, S04 conc. JL S- (n-cctil) -H, n Analogously to example 1 a) and example 2, 16.73 g (0.1 mol) of 2-mercaptobenzothiazole are reacted with 20.43 g (0.1 mol) of l-octylthio-2-propanol (18915-86). -1, Phillips Petroleum, US patent specification 2. 863. 799), obtaining 32.9 g of an orange-brown oil (yield, 93% of theory). Elemental analysis: 61.29% of C (calculated 61.14); 7.74% of H (calculated 7.70); 4.15% of N (calculated 3.96); approx. 27% of S (calculated 27.20, problematic determination of S). Example 4 N - N (tero-dafecn.) S ^^ s-. ^ s ^ s- (tero- rxteci 1) s Analogously to example la) and examples 2 and 3, 60.7 g (0.4 mol) of 2,5-dimercapto-1,3,4-thia-diazole are reacted with 208.4 g (0.8 mol) ) of the product of Example Ib, obtaining 221 g of a pale yellow transparent oil, of medium viscosity (yield, 87% of the theory). nD20.- 1.5488; elemental analysis: 60.35% of C (calculated 60.51); 9.81% of H (calculated 9.84); 4.44% of N (calculated 4.41); approx. 25% of S (calculated 25.24, problematic determination of S). Example 5 ^ - S- (tero-raul) -Mtera-irnil) O0- S- (teD- nc-nil) a) Analogously to example la and examples 2-4, 88 g (0.5 mole) of 2 are reacted -mercaptobenzothiazole with 188.5 g (0.5 mol) of the product of example 5b), obtaining 259.7 g of a clear yellow oil of medium viscosity (yield, 99% of theory). nD20: 1.5699; elemental analysis: 64.04% of C (calculated 63.95); 9.16% H (calculated 9.01); 2.70% of N (calculated 2.66); approx. 24.50% of S (calculated 24.38, problematic determination of S). b) The starting material is prepared as follows: Dissolve 337.5 g (2 moles) of tert-nonylmercaptan and 80 g (2 moles) of sodium hydroxide in 700 ml of ethanol and 320 ml of water, and homogenize by heating to 50 ° C. At 25 ° C, 93.4 g of epichlorohydrin are added dropwise over 1.5 hours. At 60 ° C, the mixture is allowed to react for 2 hours and the milky emulsion formed is then concentrated by evaporation. The residue is dissolved with approx. 100 ml of hexane and washed with 100 ml of water and 3 ml of water and 3 ml of acetic acid and again with water until neutral (pH 6). The organic phase is concentrated by evaporation and dried under reduced pressure (130 ° C / ca. 0.03 mbar), obtaining 378 g of a slightly viscous transparent colorless oil (yield, about 100% of theory). DN20: 1.4985; elemental analysis: 67.06% C (calculated 66.96); 11.96% of H (calculated 11.77). Example 6 HjS04 conc.

Analogously to examples la), 2-4 and 5a, 105.3 g (0.7 moles) of 2,5-dimercapto-1,3,4-thiadiazole are reacted with 527 g (1.4 moles) of the product of example 5b), obtaining 580 g of a pale yellow transparent oil (yield, 95% of the theory). nD20: 1,5496, - elemental analysis: 60.39% of C (calculated 60.91); 9.91% of H (calculated 9.99); 3.32% of N (calculated 3.23); approx. 26% of S (calculated 25.87, problematic determination of S). . , Example 7 / - n-daderil) Analogously to examples la), 2-4, 5a) and 6, 16.7 g (0.1 mol) of 2-mercaptobenzothiazole are reacted with 46.1 g (0.1 mol) of 1,3-bis (dodecytium) -2-propanol [59852-53-8, US patent specification 3,954,839], obtaining 59.6 g of an orange-brown oil (yield 98% of theory). Elemental analysis: 67.06% of C (calculated 66.94); 9.86% of H (calculated 9.75); 2.10% of N (calculated 2.30); 21% of S (calculated 21, 02). Example 8 ) a) Analogously to examples la), 2-4, 5a), 6 and 7, 38 g (0.25 mol) of 2,5-dimercapto-1,3,4-thiadiazole are reacted with 230.45 g (0.5 mol) of the product of example 8b), obtaining 244 g of a pale yellow transparent oil of medium viscosity (yield, 94% of theory). nD20: 1.5396; elemental analysis: 64.04% of C (calculated 64.93); 10.63% H (calculated 10.70); 2.93% of N (calculated 2.70); approx. 22% of S (calculated 21.66, problematic determination of S). b) The starting material is prepared as follows: Analogously to Example 8b), 426 g (2 moles) of tert-dodecyl mercaptan are reacted with 93.5 g (1 mole) of epichlorohydrin and 80 g (2 moles) of sodium hydroxide, yielding 460 g of a clear, colorless oil. of medium viscosity (yield, 99% of the theory). nD20: 1.4956. Example 9 a) Analogously to examples la), 2-4, 5a), 6,7 and 8a), 8.8 g (0.05 moles) of 2-mercaptobenzothiazole are reacted with 23.2 g (0.05 moles) ) of the product of example 9b). 26 g of crude product are purified by column chromatography with 200 g of silica gel (toluene / ethyl acetate) to obtain 10.7 g of a clear, pale yellow oil of medium viscosity. nD20: 1,5534; elemental analysis: 58.48% of C (calculated 58.69); 7.82% of H (calculated 7.72); 2.44% of N (calculated 2.28); approx. 21% of S (calculated 20.89, problematic determination of S). b) Preparation of the starting material: 9.4 g (0.1 mol) of epichlorohydrin are added dropwise over 30 minutes to 40.8 g (0.2 mol) of iso-octyl 2-mercaptoacetate * and 21.2 g (0.211 mol) of triethylamine in 100 ml of toluene. This mixture is then stirred for 12 hours at 60-110 ° C. The product, concentrated by evaporation, is dissolved in 100 ml of ethyl acetate and then washed with 100 ml of water (+ some 2N HCl) and concentrated again by evaporation. A small amount (approximately 11 g) of the unreacted reactant (IOMA *) is distilled off at reduced pressure (75-85 ° C / approx. 0.03 mbar), yielding 34.3 g of an oil as the main product. colorless transparent medium viscosity (yield, 74% of theory).

Elemental analysis: 57.22% of C (calculated 59.45); 9.31% of H (calculated 9.54); approx. 13% of S (calculated 13.80, problematic determination of S). *) thioglycolic acid ester of branched chain octanols (IOMA). Example 10 Analogously to examples la), 2 - 4, 5a), 6, 7, 8a) and 9a), 7.6 g (0.05 mole) of 2,5-dimercapto-1,3,4-thiadiazole were reacted with 46.5 g (0.1 mole) of the product of example 9b). 48 g of crude product are purified by column chromatography with 300 g of silica gel (toluene / ethyl acetate), obtaining 22 g of a clear yellow oil of medium viscosity. nD20: 1.5224; elemental analysis: 55.88% of C (calculated 55.24); 8.70% of H (calculated 8.31); 2.32% of N (calculated 2.68); approx. 20% of S (calculated 21.55, problematic determination of S). Example 11 Nfe? Qa of is? Te-XB a) Analogously to example la) 123 g are reacted (0.7 mol) of 2-mercaptobenzothiazole with 203 g (0.7 mol) of the product from example 11b), obtaining 299 g of a yellow oil of average viscosity (yield, 97% of theory). nD20: 1.5682; elemental analysis: 62.90% of C (calculated 62.82); 8.57% of H (calculated 8.48); 3.33% of N (calculated 3.19); approx. 21.97% of S (calculated 21.87). b) the starting material is prepared as follows: , m_ .lu; CIte? > «? -? L) -S 433 g (2 moles) of tert-nonyl glycidyl thioether [for the preparation thereof see US Pat. No. 4,931,576], are added to a solution consisting of 40 g (1 mole) of sodium hydroxide on 31 n-butanol for 15 minutes at 60-65 ° C. This mixture is stirred for 4 hours at approx. 60 ° C and the excess n-butanol is removed by distillation. After the addition of 300 ml of special boiling alcohol (b.p. 60-90 ° C), the product is washed with dilute hydrochloric acid until neutral pH. Concentrating the organic phase by evaporation and then drying the product under reduced pressure (120 ° C / 0.05 mbar) yields 564 g of a clear yellow oil of medium viscosity (yield, 97% of theory). DN20: 1.4756; elemental analysis: 66.15% of C (calculated 66.15); 11.76% of H (calculated 11.80); 11.30% of S (calculated 11.04). Example 12 s- (tepraiii) «Htero-mul. Isatet-cd N mixture (rrf tílK) - T / ^ 0- (rrtutíl) (tacoírniD-S / S ¿MteK rnil) Analogously to example la), 60 g (0.4 mols) of 2,5-dimercapto-1,3,4-thiadiazole are reacted with 232 g (0.8 mols) of the product of example 11b), yielding 265 g. g of a transparent yellow oil of medium viscosity (yield, 95% of theory). nD20: 1.5364; elemental analysis: 58.48% of C (calculated 58.75); 9.75% of H (calculated 9.57); 4.12% of N (calculated 4.03); 23.23% of S (calculated 23.06). Example 13 5b) N-N (Tferc-? Mil) -S - '? -feseüa de is? -reros S- (te? Mrnil) 75 g (0.5 mole) of 2,5-dimercapto-1,3,4-thiadiazole and 4.8 g (5 mole%) of p-toluenesulfonic acid are added to a solution consisting of 188 g (0.degree. , 5 moles) of the product of example 5b) in 600 ml of toluene. This mixture is refluxed for 1 hour in a water separator and then the toluene is removed by distillation. The crude product is dissolved in 300 ml of special boiling alcohol (bp 60-90 ° C), washed to neutral pH, concentrated by evaporation and dried under reduced pressure. (110 ° C / 0.05 mbars, 30 minutes), obtaining 244 g of a viscous transparent oil, yellow in color, which has a slightly unpleasant odor (yield, 96% of theory). nD20: 1.5834; elemental analysis: 54.33% of C (calculated 54.28); 8.73% of H (calculated 8.71); 5.66% of N (calculated 5.50); 32.32% of S (calculated 31.50).

Example 14 A solution consisting of 104 g of 15% hydrogen peroxide (0.5 mol) is added dropwise over 30 minutes approx. at 30 ° C, to a solution consisting of 254 g (0.5 moles) of the product of example 13 in 250 ml of acetone. This mixture is stirred for 1 hour at 50 ° C and then charged to room temperature with sodium bisulfite solution (39%) until it is no longer possible to detect the peroxide. The acetone is then removed by distillation and the crude product is dissolved in 300 ml of a special boiling alcohol (bp 60-90 ° C), washed with water, concentrated by evaporation and dried under reduced pressure. (100 ° C / 0.04 mbars, 30 minutes), obtaining 234 g of a transparent, viscous yellow oil (yield, 92% of theory). nD20: 1.5810; elemental analysis: 54.16% of C (calculated 54.39); 8.49% H (calculated 8.53); 5.45% of N (calculated 5.52); 31.51% of S (calculated 31.56).

Example 15 Anti-wear test: To verify the suitability of the anti-wear additive, the standard method ASTM standards D-2783-81 is applied, using a four-ball Shell analyzer. The base oil used is Stock 305 from Mobil, to which the compound according to the respective example mentioned is added, in the amount indicated in table I. The SD diameter (in mm) of the wear trace is determined at 40 kg load and 1440 rpm after 1 hour of testing at 100 ° C. The results obtained are summarized in table I: Table

Claims (12)

1. CLAIMS 1. A compound of formula wherein R x is hydrogen or alkyl of 1 to 20 carbon atoms, - R 2 is a substituent of the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, bicycloalkyl of 7 to 12 carbon atoms , phenyl, alkylphenyl of 7 to 18 carbon atoms, naphthyl and phenylalkyl of 7 to 9 carbon atoms, which substituent may be substituted with one or more substituents of the group consisting of amino, carboxyl and hydroxyl and / or may be interrupted by one or more bivalent radicals from the group consisting of -O-, -NRS-, -C (= 0) -0-, -0-C (= 0) -, -C (= 0) -NR6-, and -NR6 -C (= 0) -; R3 and R4 are hydrogen or have the meanings of R2 with the proviso that R2 is alkyl of 4 to 20 carbon atoms if R3 and R4 are hydrogen; Rs is hydrogen or partial formula groups: wherein R2, R3 and R4 have the meanings cited or have the meaning of R2; and R6 is hydrogen or alkyl of 1 to 4 carbon atoms.
2. 2. A compound of formula I and II according to claim 1, wherein Rx is hydrogen; R2 is a substituent of the group consisting of alkyl of 1 to 20 carbon atoms, phenyl, alkylphenyl of 7 to 18 carbon atoms and phenylalkyl of 7 to 9 carbon atoms, which substituent can be substituted with one or more substituents of the group formed by amino, carboxyl and hydroxyl and / or may be interrupted by one or more bivalent radicals from the group consisting of -O-, -NR6-, -C (= 0) -0-, -0-C (= 0) -, -C (= 0) -NR6- and -NRß-C (= 0) -; R3 and R4 are hydrogen or have the meanings of R2, with the proviso that R2 is alkyl of 4 to 20 carbon atoms if R3 and R4 are hydrogen; Rs has the meanings of R2 or is a group of partial formula (A) and (B), in which R2, R3 and R4 have the meanings cited, - and Rβ is hydrogen or alkyl.
3. 3. A compound of formula I and II according to claim 1, wherein Rt is hydrogen; R 2 is a substituent of the group consisting of alkyl of 1 to 20 carbon atoms, phenyl, alkylphenyl of 7 to 18 carbon atoms and phenylalkyl of 7 to 9 carbon atoms, which substituent can be interrupted with one or more bivalent radicals of the group formed by -O-, -C (= 0) -0- and -OC (-O) -; R3 and R4 are hydrogen or have the meanings of R2, with the proviso that R2 is alkyl of 4 to 20 carbon atoms if R3 and R4 are hydrogen; Rs has the meanings of R2 or is a group of partial formula (A) and (B), in which R2, R3 and R4 have the meanings cited.
4. 4. A compound of formula I and II according to claim 1, wherein Rx is hydrogen; R2 is alkyl of 1 to 20 carbon atoms, which may be interrupted with a bivalent radical of the group consisting of -0-, -C (= 0) -0- and -0-C (= 0) -; R3 and R4 are hydrogen or have the meanings of R2, with the proviso that R2 is alkyl of 4 to 20 carbon atoms if R3 and R4 are hydrogen; R5 has the meanings of R2 or is a group of partial formula (A) and (B), in which R2, R3 and R4 have the meanings cited.
5. 5. A compound of formula I 'according to claim 1: wherein R2 is alkoxycarbonylmethyl of 4 to 18 carbon atoms, R3 is alkoxycarbonylmethythiomethyl of 4 to 18 carbon atoms and R4 is hydrogen; or R2 is alkyl of 5 to 12 carbon atoms and R3 alkylthiomethyl of 5 to 12 carbon atoms, and R4 is hydrogen, - or R2 is alkoxycarbonylmethyl of 4 to 18 carbon atoms, R3 is hydrogen and R4 is alkoxycarbonylmethythiomethyl of 4 to 18 carbon atoms; or R2 is alkyl of 5 to 12 carbon atoms, R3 is hydrogen and R4 is alkylthiomethyl of 5 to 12 carbon atoms.
6. 6. A compound of formula II 'according to claim 1: wherein R2 and R'2 are alkoxycarbonylmethyl of 4 to 18 carbon atoms, R3 and R'3 are alkoxycarbonylmethythiomethyl of 4 to 18 carbon atoms, and R4 and R'4 are hydrogen, - or R2 and R'2 are alkyl from 5 to 12 carbon atoms, R3 and R'3 are alkylthiomethyl of 5 to 12 carbon atoms, and R4 and R'4 are hydrogen; or R2 and R'2 are alkoxycarbonylmethyl of 4 to 18 carbon atoms, R3 and R'3 are hydrogen, and R4 and R'4 are alkoxycarbonylmethythiomethyl of 4 to 18 carbon atoms; or R 2 and R 2 are alkyl of 5 to 12 carbon atoms, R 3 and R 3 are hydrogen and R 4 and R 4 are alkylthiomethyl of 5 to 12 carbon atoms.
7. 7. A compound of formula I 'according to claim 5, wherein R2 is isooctyloxycarbonylmethyl, R3 is isooctyl-oxycarbonylmethythiomethyl, and R4 is hydrogen; or R 2 is tert-nonyl, R 3 is tert-nonyl thiomethyl and R 4 is hydrogen; or R 2 is isooctyloxycarbonylmethyl, R 3 is hydrogen and R 4 is isooctyloxycarbonylmethythiomethyl; or R2 is tert-nonyl, R3 is hydrogen and R4 is tert-nonylthiomethyl.
8. 8. A compound of formula II 'according to claim 6, wherein R2 and R'2 are isooctyloxycarbonylmethyl, R3 and R'3 are isooctyloxycarbonylmethythiomethyl and R4 and R'4 are hydrogen, - or R2 and R'2. are tert-nonyl, R3 and R'3 are tert-nonylthiomethyl and R4 and R'4 are hydrogen, - or R2 and R'2 are isooctyloxycarbonylmethyl of 5 to 10 carbon atoms, R3 and R'3 are hydrogen and R4 and R'4 are isooctyloxycarbonylmethylthio, - or R2 and R'2 are tert-nonyl of 5 to 10 carbon atoms, R3 and R'3 are hydrogen and R4 and R'4 are tert-nonylthiomethyl.
9. 9. A composition, which contains a compound of formula I or II according to claim 1, or mixtures thereof, in combination with a base oil of viscosity suitable for lubrication or with fuels.
10. 10. A concentrate, which contains an oleo-philic solvent and at least one compound of formula I or II according to claim 1, or mixtures thereof as well as other optional additives.
11. 11. A method for improving the performance of lubricants or lubricating or combustible greases, which comprises the addition of at least one compound of formula I or II or mixtures thereof according to claim 1.
12. 12. Use of a compound according to claim 1, as an additive in lubricants, hydraulic fluids or for machining metals, and in fuels. SUMMARY This invention relates to compounds which are suitable as ash-free anti-wear additives, and anti-oxidants, to lubricating compositions containing said compounds as well as to their use. Particularly preferred are the compounds of formula In the preferred compounds I ', R 2 is isooctyloxycarbonylmethyl, R 3 is isooctyloxycarbonylmethythiomethyl, and R 4 is hydrogen; or R 2 is tert-nonyl, R 3 is tert-nonyl thiomethyl and R 4 is hydrogen, - or R 2 is isooctyloxycarbonylmethyl, R 3 is hydrogen and R 4 is isooctyloxycarbonylmethythiomethyl; or R2 is tert-nonyl, R3 is hydrogen and R4 is tert-nonylthiomethyl. In the preferred compounds II ', R2 and R'2 are isooctyloxycarbonylmethyl, R3 and R'3 are isooctyloxycarbonylmethythiomethyl and R4 and R'4 are hydrogen; or R2 and R'2 are tert-nonyl, R3 and R'3 are tert-nonylthiomethyl and R4 and R'4 are hydrogen, - or R2 and R'2 are isooctyloxycarbonylmethyl, R3 and R'3 are hydrogen and R4 and R 4 are isooctyloxycarbonylmethylthio; or R2 and R'2 are tert-nonyl, R3 and R'3 are hydrogen and R4 and R'4 erc-nonylthiomethyl.