FR2629817A1 - 3,5-Dialkyl-4-hydroxybenzyl hydrocarbyl sulphides and polysulphides, their preparation and their use as antioxidising additives - Google Patents
3,5-Dialkyl-4-hydroxybenzyl hydrocarbyl sulphides and polysulphides, their preparation and their use as antioxidising additives Download PDFInfo
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- FR2629817A1 FR2629817A1 FR8804799A FR8804799A FR2629817A1 FR 2629817 A1 FR2629817 A1 FR 2629817A1 FR 8804799 A FR8804799 A FR 8804799A FR 8804799 A FR8804799 A FR 8804799A FR 2629817 A1 FR2629817 A1 FR 2629817A1
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- butyl
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- benzyl
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- 229920001021 polysulfide Polymers 0.000 title claims abstract description 10
- 239000000654 additive Substances 0.000 title abstract description 5
- 230000003064 anti-oxidating effect Effects 0.000 title abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- -1 hydrocarbyl sulphide Chemical class 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 22
- 150000008117 polysulfides Polymers 0.000 claims description 8
- 239000005077 polysulfide Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- KQPYUXWQANMRLB-UHFFFAOYSA-N 2,6-ditert-butyl-4-(phenylsulfanylmethyl)phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSC=2C=CC=CC=2)=C1 KQPYUXWQANMRLB-UHFFFAOYSA-N 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N Dibenzyl sulphide Natural products C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 229920000620 organic polymer Polymers 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 4
- 125000002877 alkyl aryl group Chemical group 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/16—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/12—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M135/24—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
La présente invention est relative à de nouveaux composés phénoliques sulfurés de formule générale
dans laquelle R1 et R2 sont des groupes alkyles ayant de 1 à 8 atomes de carbone.The present invention relates to novel sulfurized phenolic compounds of the general formula
wherein R1 and R2 are alkyl groups having 1 to 8 carbon atoms.
R1 et R2 peuvent être identiques ou différents.R1 and R2 may be the same or different.
R3 est un groupe alkyle de 1 à 20 atomes de carbone, un groupe cycloaikyle ayant de 5 à 12 atomes de carbone, un groupe phényle ou naphtyle, éventuellement substitué par un ou plusieurs groupes alkyles de 1 à 20 atomes de carbone chacun, ou un groupe alkylaryle de 7 à 20 atomes de carbone ; n est un nombre de 1 à 5.R3 is an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl or naphthyl group, optionally substituted with one or more alkyl groups of 1 to 20 carbon atoms each, or a alkylaryl group of 7 to 20 carbon atoms; n is a number from 1 to 5.
De préférence au moins un des groupes R1 et R2 est un groupe tert butyle.Preferably at least one of R1 and R2 is a tert-butyl group.
Des composés de structure (I) sont par exemple: - le diméthyl-3,5 hydroxy-4 benzyl isobutylthioéther - le diméthyl-3,5 hydroxy-4 benzyl tert.butylthioéther - le diméthyl-3,5 hydroxy-4 benzyl phénylthioéther - le diméthyl-3,5 hydroxy-4 benzyl benzylthioéther - le diméthyl-3,5 hydroxy-4 benzyl tert.nonylthioéther - le méthyl-3 tert.butyl-5 hydroxy-4 benzyl tert.butylthioéther - le méthyl-3 tert.butyl-5 hydroxy-4 benzyl isobutylthioéther - le méthyl-3 tert.butyl-5 hydroxy-4 benzyl phénylthioéther - le méthyl-3 tert.butyl-5 hydroxy-4 benzyl benzylthioéther - le méthyl-3 teft.butyl-5 hydroxy-4 benzyl tert.nonylthioéther - le ditert.butyl-3,5 hydroxy-4 benzyl tert.butylthioéther - le ditert.butyl-3,5 hydroxy-4 benzyl phénylthioéther - le ditert.butyl-3,5 hydroxy-4 benzyl benzylthioéther - le ditert.butyl-3,5 hydroxy-4 benzyl tert.nonylthioéther - le méthyl-3 tert.butyl-5 hydroxy-4 benzyl tert.butyldisulfure - le méthyl-3 tert.butyl-5 hydroxy-4 benzyl phényldisulfure - le méthyl-3 tert.butyl-5 hydroxy-4 benzyl benzyldisulfure - le méthyl-3 tert.butyl-5 hydroxy-4 benzyl teft.nonyldisulfiire - le ditert.butyl-3,5 hydroxy-4 benzyl benzyldisulfure - le ditert.butyl-3,5 hydroxy-4 benzyl tert.nonyldisulfure - le ditert.buttl-3,5 hydroxy-4 benzyl tert.butyltrisulfure - le ditert.butyl-3,5 hydroxy-4 benzyl phényltrisulfure - le ditert.butyl-3,5 hydroxy-4 benzyl benzyltrisulfure et - le dîtert.butyl-3,5 hydroxy-4 benzyl tert.nonyltétrasulfure.Compounds of structure (I) are for example: - 3,5-dimethyl-4-hydroxy-benzyl isobutylthioether - 3,5-dimethyl-4-hydroxy-benzyl tert.butylthioether - 3,5-dimethyl-4-hydroxy benzyl phenylthioether - 3,5-dimethyl-4-hydroxy-benzyl benzylthioether-3,5-dimethyl-4-hydroxy-benzyl tert.nonylthioether-3-methyl-5-tert-butyl-4-hydroxy-benzyl tert.butylthioether-3-methyl-tert-butyl 5-hydroxy-4-benzyl isobutylthioether - 3-methyl-5-tert-butyl-4-hydroxy-benzyl phenylthioether - 3-methyl-5-tert-butyl-4-hydroxy-benzyl benzylthioether - 3-methyl-5-tetbutyl-4-hydroxy-4-hydroxy benzyl tert.nonylthioether - 3,5-ditert-butyl-4-hydroxy-benzyl tert.butylthioether - 3,5-ditert-butyl-4-hydroxy-benzyl phenylthioether - 3,5-ditert-butyl-4-hydroxy benzyl benzylthioether - the 3,5-ditert-butyl-4-hydroxy-benzyl tert.nonylthioether-3-methyl-5-tert-butyl-4-hydroxy-benzyl tert.butyldisulfide-3-methyl-5-tert-butyl-4-hydroxy-benzyl phenyldi isulfide - 3-methyl-5-tert-butyl-4-hydroxy-benzyl benzyldisulphide - 3-methyl-5-tert-butyl-4-hydroxy-benzyl-tert.-n-butyl disulfide - 3,5-ditert-butyl-4-hydroxy-benzyl benzyldisulfide - ditert 3,5-butyl-4-hydroxy-benzyl tert.-n-butyl disulphide - ditert.buttl-3,5-hydroxy-4-benzyl tert.butyltrisulfide - 3,5-ditert-butyl-4-hydroxy-benzyl phenyltrisulfide - ditert.-butyl-3 4-hydroxy-benzyl benzyltrisulfide and 3,5-di-tert-butyl-4-hydroxy-4-benzyl tert.nonyltetrasulfide.
Les composés de formule (I) peuvent être obtenus par réaction d un halogeno méthyl-4 dialkyl-2,6 phénol (II)
où X représente un halogène, par exemple Cl ou Br, Rl et R2 sont définis comme dans la formule (I): - soit avec un mercaptate de métal alcalin : R3 - S- N.I+ pour l'obtention de thioéthers, - soit avec un mercaptate polysulfure de métal alcalin : R3 S NI+ pour l'obtention de polysulfures, où R3 est défini comme dans la formule (I), NI est un métal alcalin et n est un nombre de 1 à 5. The compounds of formula (I) can be obtained by reaction of a halogeno-methyl-4-dialkyl-2,6-phenol (II)
where X represents a halogen, for example Cl or Br, R1 and R2 are defined as in formula (I): either with an alkali metal mercaptate: R3-S-N.I + for obtaining thioethers, - or with an alkali metal polysulfide mercaptate: R 3 S NI + for obtaining polysulfides, where R 3 is defined as in formula (I), NI is an alkali metal and n is a number from 1 to 5.
Les mercaptate-polysulfures de métaux alcalins peuvent être obtenus par réaction du soufre sur un mercaptate de métal alcalin. Une telle réaction est décrite par exemple par KULIEV, ZEINALOVA, GASANOV et ALIEV dans le "Journal of
Organic Chemistry of the USSR" 14, 661 (1978) pour la synthèse de disulfures d'alkyle. Elle consiste à introduire lentement une quantité stoechiométrique de soufre finement divisé dans une solution d'alkylmercaptate de sodium dans l'isopropanol à une température de 600C. Le mélange réactionnel est ensuite porté à 75-800C pendant 5 heures.The mercaptate polysulfides of alkali metals can be obtained by reacting sulfur with an alkali metal mercaptate. Such a reaction is described for example by KULIEV, ZEINALOVA, GASANOV and ALIEV in the "Journal of
Organic Chemistry of the USSR 14,661 (1978) for the synthesis of alkyl disulfides, which consists in slowly introducing a stoichiometric amount of finely divided sulfur into a solution of sodium alkylmercaptate in isopropanol at a temperature of 600.degree. The reaction mixture is then brought to 75-800C for 5 hours.
L'invention concerne également l'utilisation des composés de formule (I) comme additifs antioxs dants pour composés organiques, par exemple pour huiles lubrifiantes hydrocarbonées, pour huiles lubrifiantes synthétiques telles que esters de diacides, esters de polyols, polyalphaoléfines, alkylbenzènes et pour polymères organiques tels que polyéthylène, polypropylène. Dans ces emplois les composés de foumule (I) sont utilisés à raison de 0,05 à 5 5S en masse, de #préférence 0,1 à 1 % en masse.The invention also relates to the use of the compounds of formula (I) as antioxidant additives for organic compounds, for example for hydrocarbon lubricating oils, for synthetic lubricating oils such as diacid esters, polyol esters, polyalphaolefins, alkylbenzenes and for polymers organic such as polyethylene, polypropylene. In these uses the compounds of formula (I) are used in a proportion of 0.05 to 5% by weight, preferably 0.1 to 1% by weight.
Les exemples suivants illustrent l'invention. Ils ne doivent en aucune manière être considérés comme limitatifs.The following examples illustrate the invention. They should in no way be considered as limiting.
EXEMPLE 1
Ditert.butyl-3,5 hydroxy-4 benzyl tert.butylthioéther (III)
Le tert.butylmercaptate de sodium est obtenu par neutralisation de 50 g (0.cl mole) de tert.butylmercaptan dissous dans 500 mi de méthanol par de la soude en pastilles en quantité stoechiométrique. Le chlorométhyl-4 ditert.butvl-2.6 phénol (160 g, 0,63 mole) est introduit progressivement dans le mélange porté à léger reflux. A la fin de l'addition. le reflux est prolongé pendant 3 heures.
Après retour à la température de l'ambiance, on ajoute 300 cm3 d'eau puis on distille l'alcool; ; le monosulfure est ensuite extrait à l'éther éthylique, lavé à l'eau et séché. Après évaporation du solvant, 175 g de sulfure (III) sont recueillis, ce qui correspond à un rendement de 90 %.Le produit visqueux jaune-clair obtenu a été analysé en RMN du proton. Les déplacements chimiques observés confirment la structure du produit
Ditert.butyl-3,5-hydroxy-4-benzyl tert.butylthioether (III)
The sodium tert.butylmercaptate is obtained by neutralization of 50 g (0.cl mole) of tert.butyl mercaptan dissolved in 500 ml of methanol with pelletized sodium hydroxide in a stoichiometric amount. 4-chloromethyl-2,6-dithiophenol (160 g, 0.63 mol) is introduced gradually into the mixture brought to light reflux. At the end of the addition. reflux is prolonged for 3 hours.
After returning to the temperature of the atmosphere, 300 cm3 of water are added and then the alcohol is distilled; ; the monosulfide is then extracted with ethyl ether, washed with water and dried. After evaporation of the solvent, 175 g of sulfide (III) are collected, which corresponds to a yield of 90%. The light yellow viscous product obtained was analyzed by proton NMR. The chemical shifts observed confirm the structure of the product
H 6 (ppm) a 5,1 b 1,45 c 3,75 d 1,35 e 7,1 EXEMPLES 2 A 6
La synthèse des sulfures des exemples 2 à 6 est réalisée selon le procédé décrit à l'exemple 1.H 6 (ppm) a 5.1 b 1.45 c 3.75 d 1.35 e 7.1 EXAMPLES 2 TO 6
The synthesis of the sulphides of Examples 2 to 6 is carried out according to the process described in Example 1.
Tableau 1
<tb> <SEP> Produit <SEP> R1 <SEP> R2 <SEP> <SEP> R3 <SEP> Rendement <SEP> (%)
<tb> Ex <SEP> 2 <SEP> IV <SEP> méthyle <SEP> tert.butyle <SEP> tert.butyle <SEP> 88
<tb> Ex <SEP> 3 <SEP> V <SEP> méthyle <SEP> tert.butyle <SEP> isobutyl#e <SEP> 91
<tb> Ex <SEP> 4 <SEP> VI <SEP> tert.butyle <SEP> tert.butyle <SEP> phényle <SEP> 85
<tb> Ex <SEP> 5 <SEP> VII <SEP> tert.butyle <SEP> tert.butyle <SEP> benzoyle <SEP> <SEP> 96
<tb> Ex <SEP> 6 <SEP> VIII <SEP> ~ <SEP> <SEP> tert.butyle <SEP> tert.butyle <SEP> tert.nonyle <SEP> (*) <SEP> 93
<tb> (*) <SEP> Mélange <SEP> -de <SEP> mercaptans <SEP> principalement <SEP> en <SEP> Cg <SEP> <SEP> dérivés <SEP> du <SEP> tripropylène.
<tb> <tb><SEP> Product <SEP> R1 <SEP> R2 <SEP><SEP> R3 <SEP> Yield <SEP> (%)
<tb> Ex <SEP> 2 <SEP> IV <SEP> methyl <SEP> tert.butyl <SEP> tert.butyl <SEP> 88
<tb> Ex <SEP> 3 <SEP> V <SEP> methyl <SEP> tert.butyl <SEP> isobutyl # e <SEP> 91
<tb> Ex <SEP> 4 <SEP> VI <SEP> tert.butyl <SEP> tert.butyl <SEP> phenyl <SEP> 85
<tb> Ex <SEP> 5 <SEP> VII <SEP> tert.butyl <SEP> tert.butyl <SEP> benzoyl <SEP><SEP> 96
<tb> Ex <SEP> 6 <SEP> VIII <SEP> ~ <SEP><SEP> tert.butyl <SEP> tert.butyl <SEP> tert.nonyl <SEP> (*) <SEP> 93
<tb> (*) <SEP> Blend <SEP> of <SEP> mercaptans <SEP> mainly <SEP> in <SEP> Cg <SEP><SEP> derivatives <SEP> of <SEP> tripropylene.
<Tb>
Les produits obtenus ont été analysés en RNIN du proton et les déplacements
chimiques observés sont en bonne concordance avec la structure des produits.The products obtained were analyzed in proton RNIN and displacements
observed chemicals are in good agreement with the structure of the products.
EXEMPLE 7
Ditert.butyl-3,5 hydroxy-4 benzyl benzyldisulfure. (IX)
Le benzylmercaptate de sodium est obtenu par réaction de 132 g (1,1 mole) de benzylmercaptan avec 45 g (1,1 mole) de soude en pastilles dissoute dans 500 mi de méthanol. De la fleur de soufre (36 g - 1,1 mole) est alors ajoutée dans la solution de benzylmercaptate de sodium vigoureusement agitée. Le mélange est alors chauffé pendant 2 heures à 600 C, puis laissé revenir à la température ambiante. 256 g (1 mole) de dérivé halogéné (II) sont introduits très lentement sous violente agitation du milieu réactionnel. La température est portée progressivement au reflux du méthanol, reflux qui est ensuite maintenu pendant deux heures. Après refroidissement on ajoute 500 cm3 d'eau, puis le méthanol est distillé. La phase organique récupérée après décantation est traitée au reflux avec 200 ml d'une solution aqueuse de soude à 10 98 pendant trois heures.EXAMPLE 7
Ditert.butyl-3,5-hydroxy-4-benzyl benzyldisulfide. (IX)
The sodium benzyl mercaptate is obtained by reaction of 132 g (1.1 moles) of benzyl mercaptan with 45 g (1.1 moles) of sodium hydroxide pellets dissolved in 500 ml of methanol. Sulfur flower (36 g - 1.1 mol) is then added to the vigorously stirred sodium benzylmercaptate solution. The mixture is then heated for 2 hours at 600 ° C. and then allowed to return to ambient temperature. 256 g (1 mole) of halogenated derivative (II) are introduced very slowly under violent stirring of the reaction medium. The temperature is brought gradually to the reflux of the methanol, reflux which is then maintained for two hours. After cooling, 500 cm3 of water are added, and then the methanol is distilled off. The organic phase recovered after decantation is refluxed with 200 ml of a 10% aqueous sodium hydroxide solution for three hours.
La phase organique est à nouveau séparée, lavée à l'eau et séchée. La masse de produit IX receuillie est de 398 g, soit un rendement de 94 %. Le produit obtenu a une teneur en soufre de 16,4 % (théorie 17,1 roc). The organic phase is separated again, washed with water and dried. The mass of product IX collected is 398 g, a yield of 94%. The product obtained has a sulfur content of 16.4% (theory 17.1 rock).
L'analyse par chromatographie en couche mince met en évidence l'absence de soufre élémentaire. Le soufre du composé IX est donc bien lié, probablement sous forme d'un mélange de mono et polysulfures correspondant statistiquement à n = 2.The analysis by thin layer chromatography shows the absence of elemental sulfur. The sulfur of compound IX is therefore well bound, probably in the form of a mixture of mono and polysulfides corresponding statistically to n = 2.
EXEMPLES 8 A 12
La synthèse des composés décrits dans les exemples 8 à 19 est réalisée selon le procédé décrit dans l'exemple 7. La valeur de n est ajustée par la quantité de soufre ajoutée au mercaptate de sodium dans la première phase de la réaction.EXAMPLES 8 TO 12
The synthesis of the compounds described in Examples 8 to 19 is carried out according to the method described in Example 7. The value of n is adjusted by the amount of sulfur added to the sodium mercaptate in the first phase of the reaction.
Tableau 2
<tb> <SEP> - <SEP> s%
<tb> <SEP> Produit <SEP> Ri <SEP> R2 <SEP> R3 <SEP> n <SEP> tr. <SEP> th. <SEP> Rendement <SEP> (7G <SEP>
<tb> <SEP> Ex <SEP> 8 <SEP> X <SEP> méthyle <SEP> tert.butyle <SEP> tert <SEP> butyle <SEP> 2 <SEP> 21,1 <SEP> 21,5 <SEP> 91
<tb> <SEP> Ex <SEP> 9 <SEP> XI <SEP> tert.butyle <SEP> tert.butyle <SEP> tert.butyle <SEP> 3 <SEP> 24,6 <SEP> 25,8 <SEP> 93
<tb> Ex <SEP> 10 <SEP> XII <SEP> tert.butyle <SEP> tert.butyle <SEP> benzyle <SEP> 3 <SEP> 22,9 <SEP> 23,7 <SEP> 95
<tb> Ex <SEP> 11 <SEP> XIII <SEP> tert.butyle <SEP> tert.butyle <SEP> isobutyle <SEP> 3 <SEP> 24,3 <SEP> 25,8 <SEP> 95
<tb> Ex <SEP> 12 <SEP> XIV <SEP> tert.butyle <SEP> tert.butyle <SEP> tert.nonyle <SEP> (*) <SEP> 2 <SEP> 14,2 <SEP> 15,6 <SEP> 96
<tb> (*) <SEP> Mélange <SEP> de <SEP> mercaptans <SEP> principalement <SEP> en <SEP> C9 <SEP> <SEP> dérivés <SEP> du <SEP> tripropylène.
<tb> <tb><SEP> - <SEP> s%
<tb><SEP> Product <SEP> Ri <SEP> R2 <SEP> R3 <SEP> n <SEP> Tr. <SEP> th. <SEP> Yield <SEP> (7G <SEP>
<tb><SEP> Ex <SEP> 8 <SEP> X <SEP> methyl <SEP> tert.butyl <SEP> tert <SEP> butyl <SEP> 2 <SEP> 21.1 <SEP> 21.5 <SEP> 91
<tb><SEP> Ex <SEP> 9 <SEP> XI <SEP> tert.butyl <SEP> tert.butyl <SEP> tert.butyl <SEP> 3 <SEP> 24.6 <SEP> 25.8 <SEP> 93
<tb> Ex <SEP> 10 <SEP> XII <SEP> tert.butyl <SEP> tert.butyl <SEP> benzyl <SEP> 3 <SEP> 22.9 <SEP> 23.7 <SEP> 95
<tb> Ex <SEP> 11 <SEP> XIII <SEP> tert.butyl <SEP> tert.butyl <SEP> isobutyl <SEP> 3 <SEP> 24.3 <SEP> 25.8 <SEP> 95
<tb> Ex <SEP> 12 <SEP> XIV <SEP> tert.butyl <SEP> tert.butyl <SEP> tert.nonyl <SEP> (*) <SEP> 2 <SEP> 14.2 <SEP> 15 , 6 <SEP> 96
<tb> (*) <SEP><SEP> Blend of <SEP> mercaptans <SEP> mainly <SEP> in <SEP> C9 <SEP><SEP>SEP> derivatives of <SEP> tripropylene.
<Tb>
Les composés X à XIV ont été analysés par chromatographie en couche mince.Compounds X to XIV were analyzed by thin layer chromatography.
La présence de soufre élémentaire n'a pas été décelée. Le soufre des composés
X à XIV a donc bien été intégré dans la chaîne polysulfure, probablement sous forme de mélange de polysulfures correspondant statistiquement à la valeur de n. Par ailleurs, les spectres de résonance magnétique nucléaire du proton sont tout à fait conformes à ceux des produits attendus. Aussi par exemple, avec
XII en RMN du proton, les déplacements chimiques suivants sont observés
X to XIV was thus integrated into the polysulfide chain, probably as a mixture of polysulfides corresponding statistically to the value of n. Moreover, the nuclear magnetic resonance spectra of the proton are entirely in line with those of the expected products. Also for example, with
XII in the proton NMR, the following chemical shifts are observed
H 6 (ppm) a 5,1 b 1,5 c 3,7-4,1-4,2 d 7,3
La présence de plusieurs signaux entre 3,7 et 4,2 ppm confirme que l'on a affaire à un mélange de polysulfures correspondant en moyenne à la valeur n = 3. H 6 (ppm) at 5.1 b 1.5 c 3.7-4.1-4.2 d 7.3
The presence of several signals between 3.7 and 4.2 ppm confirms that we are dealing with a mixture of polysulfides corresponding on average to the value n = 3.
EXEMPLE 13
Action antioxvdante dans les huiles minérales.EXAMPLE 13
Antioxidant action in mineral oils.
L'efficacité antioxydante des composés selon l'invention a été établie selon la méthode PSA-RENAULT 1517. Dans cet essai, 300 ml d'huile disposés dans un Erlenmeyer sont portés dans un bain d'huile à la température de 1300C pendant 200 heures. Durant toute la durée de l'essai, un barbotage de 10-l/h d'air est assuré à débit constant. En fin d'essai l'huile est analysée du point de vue augmentation de la viscosité, acidité et teneur en dépôts. Les résultats sont indiqués sur le tableau 3. Les additifs sont utilisés à la dose de 0,5 W en masse dans une huile minérale constituée d'un mélange d'huile minérale 350 Neutral
Solvent et de Bright Stock Solvent ayant une viscosité de 11,3 mm2/s à 1000C et de 101,4 mm2/s à 400C correspondant à un indice de viscosité de 97. The antioxidant efficacy of the compounds according to the invention was established according to the PSA-RENAULT method 1517. In this test, 300 ml of oil arranged in an Erlenmeyer flask are carried in an oil bath at a temperature of 1300C for 200 hours. . Throughout the duration of the test, a bubbling of 10-l / h of air is ensured at constant flow. At the end of the test the oil is analyzed from the point of view of increasing viscosity, acidity and deposit content. The results are shown in Table 3. The additives are used at a dose of 0.5 W by weight in a mineral oil consisting of a 350 Neutral mineral oil mixture.
Solvent and Bright Stock Solvent having a viscosity of 11.3 mm2 / s at 1000C and 101.4 mm2 / s at 400C corresponding to a viscosity index of 97.
Tableau 3
<tb> Additifs <SEP> Sans <SEP> VII <SEP> VIII <SEP> XIV
<tb> Augmentation <SEP> de <SEP> viscosité <SEP> Wo <SEP>
<tb> <SEP> à <SEP> 1000C <SEP> 5,6 <SEP> 3,9 <SEP> 4,5 <SEP> 3,2
<tb> <SEP> à <SEP> 400C <SEP> <SEP> 9,3 <SEP> 5,1 <SEP> 6,8 <SEP> 4,2
<tb> Acidité <SEP> en <SEP> fin <SEP> d'essai <SEP> 2,6 <SEP> 1,1 <SEP> 0,7 <SEP> 0,6
<tb> <SEP> (mg <SEP> NOH/g) <SEP>
<tb> Insolubles <SEP> (ro <SEP> <SEP> masse) <SEP> 0,22 <SEP> <SEP> 0,07 <SEP> 0,05 <SEP> 0*14 <SEP>
<tb>
EXEMPLE 14
Cet exemple montre le comportement du produit VIII de l'exemple 6 en tant qu'agent stabilisant contre la thermooxydation des polyoléfines.La méthode consiste à mesurer le temps d'inhibition de la réaction exothermique d'oxydation en présence d'oxygène ,ur à 2100C. Après mélangeage sur mélangeur Haake
Rheocord EUS à 1800C pendant 5 minutes à 32 tours/minute d'un polyéthylène vierge de moyenne densité (d = 0,948) avec le produit VIII, on mesure le temps d'induction du mélange par analyse thermique différentielle sous oxygène à 2100C. Des essais comparatifs sont effectués avec des produits commerciaux.<tb> Additives <SEP> Without <SEP> VII <SEP> VIII <SEP> XIV
<tb> Increase <SEP> of <SEP> Viscosity <SEP> Wo <SEP>
<tb><SEP> to <SEP> 1000C <SEP> 5.6 <SEP> 3.9 <SEP> 4.5 <SEP> 3.2
<tb><SEP> to <SEP> 400C <SEP><SEP> 9.3 <SEP> 5.1 <SEP> 6.8 <SEQ> 4.2
<tb> Acidity <SEP> in <SEP> end <SEP> assay <SEP> 2.6 <SEP> 1.1 <SEP> 0.7 <SEP> 0.6
<tb><SEP> (mg <SEP> NOH / g) <SEP>
<tb> Insoluble <SEP> (ro <SEP><SEP> mass) <SEP> 0.22 <SEP><SEP> 0.07 <SEP> 0.05 <SEP> 0 * 14 <SEP>
<Tb>
EXAMPLE 14
This example shows the behavior of the product VIII of Example 6 as a stabilizing agent against the thermooxidation of polyolefins. The method consists in measuring the inhibition time of the exothermic oxidation reaction in the presence of oxygen. 2100C. After mixing on Haake mixer
Rheocord EUS at 1800C for 5 minutes at 32 revolutions / minute of a medium density virgin polyethylene (d = 0.948) with the product VIII, the induction time of the mixture is measured by differential thermal analysis under oxygen at 2100C. Comparative tests are carried out with commercial products.
Les résultats obtenus sont indiqués dans le tableau 4. The results obtained are shown in Table 4.
Tableau 4
<tb> <SEP> Teneur <SEP> temps <SEP> induction
<tb> Antioxydant <SEP> antioxydant <SEP> à <SEP> 2100C
<tb> <SEP> (ppm) <SEP> (min)
<tb> Triméthyl-1,3,5 <SEP> tris-2,4,6
<tb> ( <SEP> ditert <SEP> .butyl-3,5 <SEP> <SEP> hydroxybenzyl-4) <SEP> 1250 <SEP> 16
<tb> benzène
<tb> Pentaerythrityl <SEP> tetrakis
<tb> [ 3 <SEP> (ditert.butyl-3,5 <SEP> hydroxy- <SEP> 1250 <SEP> 17
<tb> phényl-4) <SEP> propionate
<tb> Produit <SEP> VIII <SEP> 1250 <SEP> 17
<tb> <tb><SEP> Content <SEP> time <SEP> induction
<tb> Antioxidant <SEP> Antioxidant <SEP> to <SEP> 2100C
<tb><SEP> (ppm) <SEP> (min)
<tb> Trimethyl-1,3,5 <SEP> Tris-2,4,6
<tb>(<SEP> ditert <SEP> .butyl-3,5 <SEP><SEP> 4-hydroxybenzyl) <SEP> 1250 <SEP> 16
<tb> benzene
<tb> Pentaerythrityl <SEP> tetrakis
<tb> [3 <SEP> (ditert.butyl-3,5 <SEP> hydroxy- <SEP> 1250 <SEP> 17
<tb> phenyl-4) <SEP> propionate
<tb> Product <SEP> VIII <SEP> 1250 <SEP> 17
<Tb>
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8804799A FR2629817A1 (en) | 1988-04-08 | 1988-04-08 | 3,5-Dialkyl-4-hydroxybenzyl hydrocarbyl sulphides and polysulphides, their preparation and their use as antioxidising additives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8804799A FR2629817A1 (en) | 1988-04-08 | 1988-04-08 | 3,5-Dialkyl-4-hydroxybenzyl hydrocarbyl sulphides and polysulphides, their preparation and their use as antioxidising additives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| FR2629817A1 true FR2629817A1 (en) | 1989-10-13 |
Family
ID=9365207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8804799A Pending FR2629817A1 (en) | 1988-04-08 | 1988-04-08 | 3,5-Dialkyl-4-hydroxybenzyl hydrocarbyl sulphides and polysulphides, their preparation and their use as antioxidising additives |
Country Status (1)
| Country | Link |
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| FR (1) | FR2629817A1 (en) |
Cited By (5)
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| EP0553890A1 (en) * | 1989-02-10 | 1993-08-04 | BASF Aktiengesellschaft | Diphenyl heteroalkyl derivatives, their preparation, as well as medicinal and cosmetic preparations prepared therefrom |
| FR2725203A1 (en) * | 1994-09-29 | 1996-04-05 | Lorraine Laminage | PROCESS FOR SYNTHESIS OF DISSYMETRIC DISULPHIDES AND NEW BENZYL DISSYMETRIC DISULPHIDES OBTAINED BY THIS PROCESS |
| FR2725202A1 (en) * | 1994-09-29 | 1996-04-05 | Lorraine Laminage | NOVEL ADDITIVES FOR LUBRICATING COMPOSITIONS, IN PARTICULAR FOR ROLLING OILS OF METALLURGIC PRODUCTS, AND METHODS FOR PREPARING THE SAME, AND LUBRICATING COMPOSITIONS THUS ADDITIVE |
| EP1146038A1 (en) * | 2000-04-12 | 2001-10-17 | Kumho Monsanto, Inc. | Novel antioxidant and method of producing the same |
| US7622507B2 (en) * | 2004-04-20 | 2009-11-24 | Acea Biosciences Inc. | Substituted organosulfur compounds and methods of using thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0553890A1 (en) * | 1989-02-10 | 1993-08-04 | BASF Aktiengesellschaft | Diphenyl heteroalkyl derivatives, their preparation, as well as medicinal and cosmetic preparations prepared therefrom |
| FR2725203A1 (en) * | 1994-09-29 | 1996-04-05 | Lorraine Laminage | PROCESS FOR SYNTHESIS OF DISSYMETRIC DISULPHIDES AND NEW BENZYL DISSYMETRIC DISULPHIDES OBTAINED BY THIS PROCESS |
| FR2725202A1 (en) * | 1994-09-29 | 1996-04-05 | Lorraine Laminage | NOVEL ADDITIVES FOR LUBRICATING COMPOSITIONS, IN PARTICULAR FOR ROLLING OILS OF METALLURGIC PRODUCTS, AND METHODS FOR PREPARING THE SAME, AND LUBRICATING COMPOSITIONS THUS ADDITIVE |
| EP0705818A1 (en) * | 1994-09-29 | 1996-04-10 | Sollac S.A. | Additives for lubrication compositions, notably for rolling oils for metallic products, processes for their preparation and lubricant compositions containing these additives |
| EP1146038A1 (en) * | 2000-04-12 | 2001-10-17 | Kumho Monsanto, Inc. | Novel antioxidant and method of producing the same |
| US7622507B2 (en) * | 2004-04-20 | 2009-11-24 | Acea Biosciences Inc. | Substituted organosulfur compounds and methods of using thereof |
| US8334316B2 (en) | 2004-04-20 | 2012-12-18 | Acea Biosciences, Inc. | Substituted organosulfur compounds and methods of using thereof |
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