Patent GB-498315-A (GB)
Title: Improvements relating to the preparation of hydroxy aromatic sulphides, selenides and tellurides
IPC: C07C391/02
Filed: 1937-07-08
Abstract: Hydroxyaromatic sulphides, selenides and tellurides are prepared by reacting a phenol or naphthol with a halide of sulphur, selenium or tellurium at a temperature between 60 and 140 DEG  C. in a boiling inert organic halide solvent while removing the hydrogen halide formed.  Phenols containing alkyl groups of 2 to 8 carbon atoms are particularly suitable as starting material and the use of polyhydroxy aromatic compounds, e.g. resorcinol, hydroquinone and their alkylated derivatives is mentioned.  In examples: (1) tertiary amylphenol dissolved in ethylenechloride is refluxed with sulphurdichloride to obtain amylphenolsulphide and a residue consisting of polymers; (2) tertiary amylphenolsulphide is reacted with sulphurdichloride in ethylenechloride to obtain a polymerized product; sulphur monochloride may be used instead of the dichloride; (3) butylphenol is reacted with sulphur monochloride as in example 1.  A petroleum lubricating oil may be added to the reaction products which are stated to be oxidation and corrosion inhibitors, or after the removal of the solvent in a vacuum.  The Specification as open to inspection under Sect. 91 comprises also the use of any inert solvent in the preparation of the hydroxyaromatic sulphides and includes the preparation of polymers having the formula <FORM:0498315/III/1> wherein R1 and R11 are alkyl groups or hydrogen and R is an alkyl group, n and n1 are integers 1 to 4 and y is an integer 1 to 6.  The products may be added to any mineral oil to improve its stability. Oils purified by extraction with the following solvents are specified: phenol, dichlorethylether, furfural, propane, nitrobenzene and crotonaldehyde.  The oils to be stabilized may contain an "oiliness agent," e.g. an organic ester, and dyes, metallic and other soaps, pour inhibitors, sludge dispersers, thickeners, isobutylene polymers, resins, rubber, fatty oils, heat thickened fatty oils, sulphurized oils, organometallic compounds, bright stocks, voltolized fats, mineral waxes, graphite or zinc oxide.  The hydroxyaromatic sulphides may be substituted by ether, aldehyde, ketone, acid, ester, amino, cyanide and sulphur, selenium and tellurium groups.  In further examples, lubricating oils stabilized with the products are subjected to various tests and the results stated.  This subject-matter does not appear in the Specification as accepted.ALSO:Hydroxyaromatic sulphides, selenides, and tellurides are prepared by reacting a phenol or naphthol with a halide of sulphur, selenium or tellurium at a temperature between 60 and 140 DEG  C. in a boiling inert organic halide solvent while removing the hydrogen halide formed.  Phenols containing alkyl groups of 2 to 8 carbon atoms are particularly suitable as starting material. These may be obtained by condensing phenols with olefines such as are obtained by cracking or dehydrogenating petroleum oils.  The use of polyhydroxy aromatic compounds, e.g. resorcinol, hydroquinone and their alkylated derivatives is mentioned. Ethylene chloride, carbontetrachloride, chloroform, tri and tetrachlorethane, trimethylene chloride, dichlorpropane, propylenechloride, propylidenedichloride, acetonechloride, di- and trichlorpropane, phenylchloride and the corresponding bromides and iodides are solvents which are specified.  In examples: (1) tertiary amyl phenol dissolved in ethylene chloride is refluxed with 0,52 molecular proportion of sulphurdichloride in ethylenechloride until all hydrogen chloride is removed, which may be facilitated by the passage of nitrogen, flue gas or other inert gas; the solvent is removed by distillation and the product subjected to fractional distillation to obtain amylphenolsulphide and a residue consisting of polymers; (2) tertiary amylphenol is reacted as in example 1 with 0,65 molecular proportion of sulphur dichloride, when a product containing an increased proportion of polymers is obtained; (3) tertiary amylphenolsulphide is reacted with sulphurdichloride in ethylenechloride to obtain a polymerized product; sulphur monochloride may be used instead of the dichloride; (4) butylphenol is reacted with sulphur monochloride as in example 1. A petroleum lubricating oil may be added to the reaction products during or after the removal of the solvent in a vacuum.  Air may be used to assist the removal of the solvent.  The products, which are stated to be oxidation and corrosion inhibitors may be subjected to fractional crystallization, extraction or precipitation with selective solvents to purify them or they may be treated with adsorptive agents such as clay.  The Specification as open to inspection under Sect. 91, comprises also the use of any inert solvent in the preparation of the hydroxyaromatic sulphides and includes the preparation of polymers having the formula <FORM:0498315/IV/1> wherein R1 and R11 are alkyl groups or hydrogen and R is an alkyl group, n and n1 are integers 1 to 4 and y is an integer 1 to 6.  The products may be added to any mineral oil to improve its stability.  Oils purified by extraction with the following solvents are specified: phenol, dichlorethylether, furfurol, propane, nitrobenzene and crotonaldehyde.  The oils to be stabilized may contain an " oiliness agent," e.g. an organic ester, and dyes, metallic and other soaps, pour inhibitors, sludge dispersers, thickeners, isobutylene polymers, resins, rubber, fatty oils, heat thickened fatty oils, sulphurized oils, organometallic compounds, bright stocks, voltolized fats, mineral waxes, graphite or zinc oxide.  The hydroxyaromatic sulphides may be substituted by ether, aldehyde, ketone, acid, ester, amino, cyanide and sulphur, selenium and tellurium groups.  In further examples, lubricating-oils stabilized with the products are subjected to various tests and the results stated.  This subject-matter does not appear in the Specification as accepted.