Patent GB-716187-A (GB)
Title: Substituted diphenyl ether sulphonate sulphides
IPC: C10L1/24
Filed: 1951-06-04
Abstract: The invention comprises aliphatic substituted diphenyl ether sulphides which contain the SO3X group bonded to a ring carbon atom, X representing hydrogen or a salt forming radical, e.g. a metal, and wherein the molecule contains a total of more than 6 aliphatic substituent carbon atoms.  The compound may be a polyaliphatic substituted compound and may contain more than 2 aliphatic substituent groups.  The preferred diphenyl ether sulphides are those having the general formula <FORM:0716187/IV (b)/1> wherein R and R1 are aliphatic radicals, M is hydrogen or one equivalent of a salt forming radical, x is at least one and not more than five, and m and n represent the number of R and R1 groups respectively attached to the diphenyl ether radicals so that there are present in the molecule more than 6 aliphatic substituent carbon atoms and preferably at least 10 of said carbon atoms.  The aliphatic radicals may be attached to the diphenyl ether radicals by carbon to carbon linkages, or through an oxygen, sulphur or nitrogen atom or a carbonyl or ester group. The diphenyl ether sulphides may be prepared by a series of reactions involving firstly the alkylation of the diphenyl ether nucleus to introduce the aliphatic substituents, secondly the introduction of the sulphonic acid radicals, thirdly the formation of the sulphur bridge, and fourthly, when required, the conversion of the free sulphonic acids into salts.  The alkylation step may be carried out by a Friedel-Crafts reaction using aluminium chloride as the catalyst, by an acid catalyst alkylation using concentrated phosphoric or sulphuric acids, or by condensation of the diphenyl ether with aliphatic alcohols or ethers.  When it is desired to attach the aliphatic radical to the diphenyl ether radicals through the intervening element or group, the Williamson reaction may be used, or the hydroxy diphenyl ether or sodium salt thereof may be reacted with an alkyl halide or an alkyl sulphate. Another method for introducing the aliphatic radicals is by mixing an aliphatic halide, e.g. a monochloro paraffin wax obtained by chlorinating paraffin wax, with diphenyl ether in the presence of an acid activated clay catalyst, such as Superfiltrol (Registered Trade Mark), Tonsil Retrol (Registered Trade Mark) or Attapulgus clay, and a small amount of zinc chloride, e.g. at a temperature in excess of 150 DEG  C. when a chloro substituted paraffin wax is used as the aliphatic halide.  The aliphatic substituent radicals may be introduced also into the diphenyl radical by condensation of the diphenyl ether with an unsaturated aliphatic compound, e.g. the unsaturated compound obtained by halogenating paraffin wax followed by dehydrohalogenation, in the presence of an acid activated clay, e.g. at temperatures from about 70 DEG  to 150 DEG  C. The aliphatic substituents which may be the same or different in the molecule may be derived from unsaturated aliphatic compounds and aliphatic halides containing more than 3 carbon atoms in straight or branched chains, e.g. isopropyl chloride, propylene, butyl chlorides such as tert.-butyl chloride, butylenes such as butylene and isobutylene, amyl chlorides, amylenes, hexyl chlorides, hexylenes, heptyl chlorides, heptylenes, octyl chlorides, octenes, nonyl chlorides, nonenes, decyl chlorides, tetradecylenes, cetyl chlorides, cetenes, oleyl chloride, oleoyl chloride and octadecenes.  The aliphatic residues may be derived also from aliphatic alcohols and ethers having any of the organic residues derived from the aliphatic halides and unsaturated aliphatic compounds just mentioned.  In a number of preparations illustrating the first step in the above series of reactions, diphenyl ether, cetene-1 and boron trifluoride are reacted to give a monocetyl diphenyl ether; diphenyl ether, octene-1 and zinc chloride are reacted to give a monocapryl diphenyl ether; diphenyl ether, an acid activated clay and caprylene-1 are reacted to give a mono- and dicapryl diphenyl ether; p-chlorodiphenyl ether, an acid activated clay and capryl alcohol are reacted to give a mono- and di-capryl chlorodiphenyl ether; diphenyl ether, an acid activated clay and 4-methyl pentanol-2 are reacted to give a product having approximately 2 of the methylpentyl radicals per diphenyl ether nucleus; diphenyl ether, an acid activated clay and capryl alcohol are reacted to give a product having an average of 3.2 capryl radicals per diphenyl ether nucleus; diphenyl, an acid activated clay and capryl alcohol are reacted to give a mono-, di- and tri-capryl diphenyl ether; diphenyl ether, an acid activated clay and dodecene-1 are reacted to give a mono- and di-lauryl diphenyl ether; diphenyl ether, an acid activated clay and cetene-1 are reacted to give a dicetyl diphenyl ether; diphenyl ether, zinc chloride and a chlorinated fuel oil (containing 18 per cent chlorine and having an average molecular weight of 200-midway between C12H25Cl and C11H23Cl) are reacted to give a poly "fuel oil" substituted diphenyl ether; diphenyl ether, an acid activated clay and diisobutylene are reacted to give a mono-, di- and tri-diisobutyl diphenyl ether; diphenyl ether, an acid activated clay and an unsaturated paraffin wax are reacted to give a paraffin wax substituted diphenyl ether and a diparaffin wax substituted diphenyl ether; diphenyl ether, an acid activated clay, zinc chloride and a chloroparaffin wax containing 18 per cent chlorine are reacted to give a paraffin wax substituted diphenyl ether; and diphenyl ether, zinc chloride, an acid activated clay and a chloro-paraffin wax containing 20 per cent chlorine are reacted to give a paraffin wax substituted diphenyl ether.  The second stage of the series of processes referred to above, i.e. the introduction of the sulphonic acid radicals, is preferably carried out by reacting the aliphatic substituted diphenyl ether with chlorsulphonic acid at a temperature in the range of from about 25 DEG  C. to 75 DEG  C.  Other sulphonating agents such as fuming sulphuric acid and sulphur trioxide may also be used.  It is preferred to introduce one sulphonic acid radical per diphenyl ether nucleus.  The third stage of the series of processes referred to above involves the formation of the sulphur bridge by reacting the aliphatic substituted diphenyl ether sulphonic acid compounds with any of the sulphur halides of the formul  SCl2, S2Cl2, SBr2 or S2Br2, or mixtures thereof, preferably at a low temperature, to form compounds having 1 or 2 sulphur atoms in the bridge.  The sulphur bridge may be increased to 3, 4 or 5 sulphur atoms by reacting the compounds having 1 or 2 sulphur atoms in the bridge with elemental sulphur.  It is not necessary for the sulphur bridge to be formed after the introduction of the sulphonic acid radicals as these two stages may be carried out in the reverse order.  The sulphonate salts of the aliphatic substituted diphenyl ether sulphides are preferably formed at the last stage, e.g. by a direct neutralization procedure with the oxides, hydroxides or carbonates of the alkali metals such as sodium, potassium and lithium, the alkaline earth metals such as barium, calcium, magnesium and strontium and other polyvalent metals such as copper, aluminium, lead, iron, tin, antimony, manganese, bismuth or nickel.  The heavy metal salts such as the zinc, cobalt, cadmium, tin, iron or mercury salts may be prepared by double decomposition with the sodium, lithium or potassium salts and the heavy metal halides.  Non-metallic salts may be prepared also, e.g. from ammonia or organic amino compounds such as mono-, di- and tri-ethanolamine, cyclohexylamine, aniline and amyl amine.  The examples illustrate the preparation of the following aliphatic substituted diphenyl ether sulphides containing sulphonic acid groups using aliphatic substituted diphenyl ethers prepared above: the calcium and barium sulphonates of capryl substituted diphenyl ether disulphides, the calcium sulphonates of cetyl substituted diphenyl ether disulphides, the calcium sulphonates of paraffin wax substituted diphenyl ether disulphides and tetrasulphides, the calcium tetrasulphonate of cetyl substituted diphenyl ether disulphides and the barium sulphonate of p, p1-bis(diisobutenoxy) diphenyl ether disulphides, and the corresponding free acids of these compounds. A number of additional compounds are referred to in the Specification.  p, p1-Bis-(diisobutenoxy) diphenyl ether is prepared by refluxing in ethyl alcohol p, p1-dihydroxy diphenyl ether, sodium hydroxide and a mixture of the isomeric monochlorodiisobutylenes obtained by the chlorination of diisobutylene.ALSO:Mineral oil composition contains a lubricating oil or a hydrocarbon fuel and an aliphatic substituted diphenyl ether sulphide which contains the SO3X group bonded to a ring carbon atom, where X represents hydrogen or one equivalent of a salt-forming group, and which contains a total of more than 6 aliphatic substituent carbon atoms (see Group IV (b)). The preferred diphenyl ether sulphides are of the general formula <FORM:0716187/III/1> wherein X has the above significance, R and R1 are aliphatic radicals, x is an interger from 1 to 5, and m and n represent the number of R and R1 radicals respectively so that there are present in the molecule more than 6 aliphatic substituent carbon atoms.  The aliphatic radicals may be attached to the diphenyl ether radicals by carbon to carbon linkages or through an oxygen, sulphur or nitrogen atom or a carboxyl or ester group.