Patent GB-808064-A (GB)
Title: Improvements in or relating to preparation of trithiones and lubricating oil compositions containing trithiones
IPC: C07C1/26
Filed: 1955-05-31
Abstract: Lubricating oils comprise, as inhibitors of bearing corrosion, 2-(alkylaryl)-substituted trithiones obtainable by reaction of sulphur under specified conditions with an alkyl aromatic hydrocarbon containing an aryl ring attached to the second carbon atom of a saturated aliphatic chain of at least 3 carbon atoms so providing a structure of the type <FORM:0808064/III/1> (see Group IV (b)).  The trithiones preferably have the general formula <FORM:0808064/III/2> wherein R is an alkyl group such as methyl, ethyl or propyl and wherein the C3 carbon atom of the trithione ring may be alkyl-substituted.  The trithiones are normally used in amounts of from about 0.01-2 weight per cent of the oil.  Other additives may be present, e.g. oil-soluble detergents such as an alkali metal or alkaline earth metal salt of a P2S5-butylene polymer reaction product, an anti-oxidant, a V.I. improver or a pour depressant. Specified 2-(alkylphenyl)-trithiones are the 2-(p-methyl-, ethyl-t-butyl and -t-amyl phenyl) trithiones and the effectiveness of a number of these and also of 2-phenyl-trithione as corrosion inhibitors is determined in a mineral lubricating oil containing a detergent additive.  Specification 679,871 is referred to.ALSO:2-Aryl-substituted trithiones are prepared by reacting an alkyl aromatic hydrocarbon, which contains an aryl ring attached to the second carbon atom of a saturated aliphatic chain of at least 3 carbon atoms to provide a structure of the type <FORM:0808064/IV (b)/1> with sulphur at a temperature of about 140-230 DEG  C. in the presence of a minor amount of a basic catalyst stable under reaction conditions.  The alkyl aromatic hydrocarbon may be cumene or an alkyl-ring-substituted cumene; also one terminal hydrogen atom in the isopropyl group of the cumene-type reagent may be replaced by an alkyl group which latter group will then appear in the trithione ring of the product; reference is also made to reagents wherein the isopropyl group is attached to aryl rings other than the mononuclear benzene ring.  The preferred alkyl aromatic hydrocarbons are p-alkyl-substituted cumenes which yield new trithiones having the general formula <FORM:0808064/IV (b)/2> wherein R is an alkyl group, e.g. methyl, ethyl or propyl and wherein an alkyl substituent may be attached to the C3 carbon atom.  The reaction is preferably carried out using excess of the hydrocarbon and in the presence of an aromatic guanidine as catalyst.  Aliphatic amines, e.g. sec. and tert. butylamines, and potassium hydroxide are other specified basic catalysts.  The catalysts are preferably used in amounts of about 0.01-2 per cent by weight.  The trithiones may be isolated by crystallization from unchanged hydrocarbon followed by washing with benzene or other light hydrocarbon solvent.  The trithiones are utilizable as corrosion inhibitors in lubricating oils (see Group III).  In typical examples: (1) a mixture of cumene, sulphur and di-o-tolyl guanidine (catalyst) is refluxed at 156 DEG  C. for 174 hours yielding 2-phenyl trithione; (2) p-cymene is similarly reacted at 180-185 DEG  C. for 11 hours to give 2-(p-methyl phenyl) trithione; (4) p-tert.-butyl cumene is similarly reacted at 184 DEG C. for 24 hours yielding p-tert.-butyl phenyl trithione.  A table lists 2-p-tolyl, 2-p-ethyl phenyl, 2-p-tert.-butylphenyl and 2-p-tert.-amyl phenyl trithiones prepared as above and for the purposes of identification their methiodides obtained by refluxing the trithiones with excess methyl iodide in n-butyl acetate.  It is stated that when dl-limonene is reacted with sulphur under the above specified conditions a double trithione in which an aromatic ring is fused to two trithione rings is obtained and that a-methyl styrene similarly reacted yields 2-phenyl-trithione. Specification 679,871, [Group III], is referred to.