Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
  • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
  • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • 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
  • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
  • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
• • 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
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
• • 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
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
• • 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
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
  • C10M2219/106—Thiadiazoles

Definitions

• This invention relates to novel thiadiazole compounds and lubricant compositions thereof prepared from the derivatives of dimercaptothiadiazole and maleic anhydride or a halosuccinate.
• Lubricating compositions containing the compound, or their metal salts provide antiwear and antioxidant properties.
• Zinc dialkyldithiophosphates have been used in lubricants as antioxidant and antiwear additives for many years (CRC Handbook of Lubrication, CRC Press, Inc., 1984).
• CRC Handbook of Lubrication CRC Press, Inc., 1984.
• phosphorous-containing compounds that may be harmful to automobile catalytic converters. It has been considered desirable to use non-phosphorouscontaining additives that can provide comparable performance.
• the novel organosulfur compounds and their metal salts used as lubricant additives can inhibit oxidation and improve extreme pressure and antiwear characteristics of a lubricant.
• Zinc and molybdenum are preferred metal ions although other metals such as nickel, cobalt, iron, tin and antimony are useful.
• the compound of the invention is defined as a compound of the structure
• Q is a bivalent thiadiazole ring moiety selected from the group consisting essentially of 1,3,4thiadiazole; 1,2,4-thiadiazole; 1,2,3-thiadiazole; and 1,2,5-thiadiazole;
• Z is a succinate group of the structure
• A is an oxygen or nitrogen atom, with the proviso: when A is oxygen a is 1, b is zero, c is 1, and d is zero; and when A is nitrogen a, b, c, and d are each 1; R, R' , R" , and R"' are each independently selected from the group consisting essentially of hydrogen, alkyl, branched or straight chain alkylene of 1 through 22 carbon atoms, arylalkyl, and heterocyclicalkylene; with the further proviso that the number one and four carbon atoms of the succinate group Z can be linked by a single A in which case when A is oxygen a, b, c, and d are zero, and when A is nitrogen a is one and b, c, and d are zero;
• M is hydrogen and x is 1 or M is a metal ion selected from from Groups lb to Vb, and transition elements of the Periodic Table and MoO 2 +2; and x is a whole number equal to the valence of M.
• Preferred compounds are those as above defined wherein M is selected from the group consisting of zinc, copper with a valence state of 2, cobalt with a valence state of 2, MoO 2 with a valence state of 2, aluminum, and antimony with a valence state of 3. It is more preferred that R, R', and R"' are each independently selected from the group consisting essentially of decyl, tridecyl, oleyl, 2-ethylhexyl, and isocetyl. It is most preferred that Q is the 1,3,4-thiadiazole moiety.
• Preferred specific compounds of the invention are: ditridecyl 2-(2-mercapto-1,3,4-thiadiazol-5-ylthio)succinate; bis [ditridecyl 2-(2-thio-1,3,4-thiadiazol-5ylthio)-succinate]-S-zinc(2+); bis[ditridecyl 2-(2-thio1,3,4-thiadiazol-5-ylthio)-succinate]-S-dibutyl; bis[dioleyl 2-(2-thio-1,3,4-thiadiazol-5-ylthio)-succinate]-S-molybdenum dioxide; bis[ditridecyl 2-(2-thio-1,3,4-thiadiazol-5-ylthio)succinate]-S-molybdenum dioxide; bis[ditridecyl 2-(2-thio1,3,4-thiadiazol-5-ylthio)-succinate]-S-cobalt(2+); bis[
• the lubricant composition of the invention comprises a major amount of a grease or oil of lubricating viscosity and a minor amount of a compound as defined above as a lubricant additive to provide enhanced properties to said grease or oil Detailed Description of the Invention
• the novel organosulfur compounds of this invention can be prepared by first reacting a 1:1 adduct of dimercaptothiadiazole and maleic anhydride with an amine or alcohol to either partially or totally convert it into an imide, amide or ester. The resulting product is then reacted with a metal salt, such as zinc oxide, zinc carbonate, zinc acetate or zinc halide, in an organic solvent at a temperature between about 50°C. and 180°C.
• the extreme pressure and antiwear properties of these compounds were evaluated by means of known methods: ASTM D 2596 and ASTM D 2266, respectively.
• the antioxidant properties of a lubricant were obtained by a versatile thermal-oxidative method known as pressure differential scanning calorimetry (PDSC).
• PDSC pressure differential scanning calorimetry
• the method measures oxidation induction time. A sample is held at an isothermal temperature in an oxidizing atmosphere. Under a set of identical conditions, the larger the oxidation induction time of a lubricant, the better is its antioxidant properties (Zeman, Stuwe and Koch, Thermochimica Acta, 80, 1-9, 1984, Elsevier Science Publisher B.V.).
• Example 1 Preparation of 2-(2-mercapto-1,3,4-thiadiazol-5-ylthio)succinic anhydride:
• the title compound was prepared in the same manner as described in Example 3.
• the reaction product is a viscous oil. Its lubricating properties in a mineral oil are listed in Table I.
• the title compound was prepared by reacting 2-(2mercapto-1,3,4-thiadiazol-5-ylthio)-succinic anhydride and oleylamine in 1:2 molar ratio in refluxing xylene for 14 hours. After removing the solvent, the reaction product is a brown, viscous oil and soluble in most non-polar solvents and mineral oils. Its IR spectrum and elemental analysis are consistent with the proposed structure.
• the title compound was prepared by refluxing a mixture of 2- (2-mercapto-1,3,4-thiadiazol-5-ylthio)-succinic anhydride and zinc carbonate in 2:1 molar ratio in xylene for three hours. Experimental details and working up of the reaction product were similar to those described in Example 3 The reaction product is a light brown, viscous oil. Its lubricating characteristic in a mineral oil are recorded in Table I and antioxidant properties by high pressure DSC are recorded in Table II.
• a solution of 10.4g. (0.025 mole) of ditridecyl 2-chlorosuccinate in 50 ml. of absolute ethanol is added dropwise to a stirred cloudy solution of 11.3 g. (0.05 mole) of the dipotassium salt of 3,5-dimercapto-1,2,4-thiadiazole (prepared according to procedure of W.A. Thaler and J.R. McDivitt; J. Org. Chem. 36, 14-18, 1971) in 200 ml. of absolute ethanol, over a period of 10 minutes. No rise in temperature is observed. The cloudy mixture is refluxed for 18 hours.
• the solvent of the filtrate is removed at 60° and reduced pressure and the yellow residue is dissolved in 100 ml. of distilled water, giving cloudy solution.
• the aquous solution is extracted with 4 x 50 ml. portions of ethyl acetate, dried with sodium sulfate and the solvent stripped off as above to obtain 18.2 g. of a yellowish brown liquid residue, which has an offensive odor similar to that of the dipotassium salt of 3,5 -dimercapto-1,2,4-thiadiazole.
• the residue is treated with 125 ml.H 2 O & 20% HCL solution to p H 1 resulting in the separation of oil.
• the oil is collected and dissolved in 150 ml. ether.
• the ether solution is washed with 3 x 50 ml. of distilled water, dried with sodium sulfate then heated on a steam bath to remove solvent.
• the liquid residue after drying at 60°c under reduced pressure weigh 8.1g. Again, it has offensive odor, but much less than before.
• the liquid residue is treated with 200 ml. of distilled water and 10% KOH to p H 14.
• the alkaline mixture is extracted with 1 x 100 ml. of either and the ether extract is in turn washed with 50 ml. of distilled water.
• the ether extract is dried with sodium sulfate then heated on a steam bath to remove solvent.
• the liquid residue is mixed with 300 ml. of distilled water, forming a pale yellow emulsion-like solution.
• the solution is heated to 55° then allowed to cool to room temperature, followed by extraction with 2 x 100 ml. of ether.
• the ether extract is dried with sodium sulfate then heated on a steam bath to remove solvent and volatiles.
• the residue is dried at 80° and 5-10 mm pressure to obtain a light yellowish brown liquid product.
• the above compound can be similarly prepared as described in Example 3 by reaction of potassium salt of ditridecyl 2-(3-mercapto-1,2,4-thiadiazol-5-ylthio)-succinate with zinc chloride in toluene.

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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)
• Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
• Lubricants (AREA)
• Plural Heterocyclic Compounds (AREA)

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• 1986
  • 1986-07-23 DE DE1986110155 patent/DE218816T1/de active Pending
  • 1986-07-23 EP EP19860110155 patent/EP0218816B1/de not_active Expired
  • 1986-07-23 DE DE8686110155T patent/DE3674528D1/de not_active Expired - Fee Related
  • 1986-07-25 CA CA000514693A patent/CA1276643C/en not_active Expired - Lifetime
  • 1986-10-13 JP JP61241580A patent/JPH0811751B2/ja not_active Expired - Lifetime
  • 1986-10-14 WO PCT/US1986/002158 patent/WO1987002358A1/en not_active Application Discontinuation
  • 1986-10-14 EP EP19860906605 patent/EP0242395A1/de not_active Withdrawn

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