Two-phase process for the preparation of azole and azoline disulfides

• US 4,351,945 A
• Filed: 02/05/1979
• Issued: 09/28/1982
• Est. Priority Date: 12/18/1978
• Status: Expired due to Term

• Current Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Original Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Inventors: Gutierrez, Antonio, Brois, Stanley J.
• Primary Examiner(s): Rollins, Alton D.
• Application Number:
  US06/009,741
• Time in Patent Office: 1,331 Days
• Field of Search: 07D/285/12, 548/130, 548/132, 548/166, 548/221, 548/329, 548/125, 548/142, 548/144, 548/186, 548/213, 548/221, 548/255, 548/265, 548/229, 548/243, 548/339, 548/377
• US Class Current: 548/130
• CPC Class Codes: C07D 235/28 Sulfur atoms
• CPC Class Codes: C07D 277/78 to a second sulphur atom
• CPC Class Codes: C07D 285/08 1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
• CPC Class Codes: C07D 285/125 with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
• CPC Class Codes: C10M 135/32 Heterocyclic sulfur, selenium or tellurium compounds
• CPC Class Codes: C10M 135/36 the ring containing sulfur and carbon with nitrogen or oxygen
• CPC Class Codes: C10M 2219/10 Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
• CPC Class Codes: C10M 2219/102 containing sulfur and carbon only in the ring
• CPC Class Codes: C10M 2219/104 containing sulfur and carbon with nitrogen or oxygen in the ring
• CPC Class Codes: C10M 2219/106 Thiadiazoles
• CPC Class Codes: C10M 2290/02 Mineral base oils; Mixtures of fractions
• CPC Class Codes: C10N 2040/08 Hydraulic fluids, e.g. brake-fluids
• CPC Class Codes: C10N 2040/20 Metal working
• CPC Class Codes: C10N 2040/252 Diesel engines
• CPC Class Codes: C10N 2040/253 Small diesel engines
• CPC Class Codes: C10N 2040/26 Two-strokes or two-cycle engines
• CPC Class Codes: C10N 2050/10 Semi-solids; greasy

Abstract

Azole and azoline disulfides useful as corrosion inhibitors and antiwear agents are prepared by the halogen-induced coupling of a thiol reactant e.g., hydrocarbyl mercaptans, with a metal azole thiolate, e.g. the potassium salt of 3,5-bis-mercapto 1,2,4-thiadiazole or 2,5-bis-mercapto 1,3,4 thiadiazole in a 2-phase reaction medium comprising a mixture of a hydrocarbon and water.

Claims

1. A process for preparing a polysulfide of a thiol-substituted azole or azoline comprising the step of halogen-induced oxidative coupling of a 2-mercapto azole or azoline or the alkali or alkaline earth metal salt thereof with a hydrocarbon substituted C₂ -C₁₀₀ polysulfide reactant in a two-phase liquid reaction medium comprising a non-polar organic solvent phase and an aqueous phase.

2. A process of claim 1 wherein said polysulfide is a dialkyl disulfide of the class consisting of t-butyl disulfide, t-octyl disulfide and t-dodecyl disulfide.

3. The process of claim 1 wherein said polysulfide is a member of the class consisting of t-octyl tetrasulfide, t-nonyl tetrasulfide and t-dodecyl tetrasulfide.

4. The process of claim 1 wherein said polysulfide is a member of the class consisting of diethyl thiuram disulfide, 2-benzothiazolyl disulfide, tetramethylthiuram disulfide and tetraethylthiuram disulfide.

5. The process of claim 1 wherein said coupling is carried out at a temperature ranging from about 0°

to about 90°

C.

6. The process of claim 1 wherein the salt of said azole is of the class consisting of alkali metals and alkaline earth metals and is present in an amount ranging from about 10% by weight of the weight of the aqueous phase to saturation of said aqueous phase.

7. The process of claim 1 wherein the oxidative coupling reagent consists of the class of chlorine, bromine, t-butyl hypochlorite, sulfuryl chloride, sulfur chloride and metal hypochlorite salts.

8. The process of claim 1 wherein said organic solvent is a member of the class of hydrocarbons consisting of pentane, hexane, heptane, octane, a neutral oil, methylene chloride, chloroform, carbon tetrachloride, and trichloroethylene.

9. The process of claim 2 wherein said azole is a 3,5-bis-mercapto-1,2,4-thiadiazole.

10. The process of claim 2 wherein said azole is 2,5-bis-mercapto-1,3,4-thiadiazole.

11. The process of claim 1 wherein said thiol-substituted azole is 2-mercapto-benzoxazole.

12. The process of claim 1 wherein said thiol-substituted azole is 2-mercapto-benzimidazole.

13. The process of claim 1 wherein said thiol-substituted azole is 2-mercapto-benzothiazole.