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*Y. /'N, X Prepared by the Reaction of an Alkali Metal Hydrosul 30 C Fide with Alkyl Or Aralkyl Halides

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*Y. /'N, X Prepared by the Reaction of an Alkali Metal Hydrosul 30 C Fide with Alkyl Or Aralkyl Halides 3,374,274 United States Patent Office Patented Mar. 19, 1968 1. 2 3,374,274 The invention can be illustrated by the following chem PROCESS FOR THE PRODUCTION OF AROMATIC ical reaction: THEOLS AND AROMATIC SULFDES James D. Spainhour, Bartlesville, Okla., assignor to R'Cl--Nas->R'SNa--NaCl Philips Petroleum Company, a corporation of wherein R' represents an aromatic radical. After com Delaware pletion of the reaction, the R'SNa compound can be No Drawing. Filed Sept. 15, 1964, Ser. No. 396,739 converted to R'SH by acidification. For example, when 10 Claims. (Cl. 260-609) R’ is phenyl, the produced R'SH compound is thiopheno. To illustrate the formation of sulfides as by-products, This invention relates to the production of aromatic 0 the following equation is illustrative of the results ob thiols. This invention also relates to the production of tained when an excess of aryl chloride is used: aromatic sulfides. In one of its aspects, the invention re lates to a process for producing an aromatic thiol and an aromatic sulfide by reacting a nuclear monohalo-sub Nuclear monohalo-substituted aromatic compounds stituted aromatic compound with an excess (above equi which can be used for the starting material according molar) of an alkali metal sulfide. In a more specific as to the invention are represented by the formulas: pect, the reaction takes place in a polar organic solvent. In a still further aspect, an aromatic thiol and a diaryl Rs. C R. C. C sulfide are produced by reacting a monohalo-substituted XN XYY aromatic compound with an excess of an alkali metal 20 sulfide in a polar organic solvent. Aromatic thiols such as thiophenol are well-known x is compounds, some of which are used commercially. For example, thiophenol is used as a rubber plasticizer and N/ N/ N/ in the reclaiming of rubber. One method which has been I II used for the manufacture of thiophenol is the reduction of benzenesulfonyl chloride with zinc dust in sulfuric acid. C Aliphatic mercaptans and aralkyl mercaptains have been - *Y. /'N, X prepared by the reaction of an alkali metal hydrosul 30 C fide with alkyl or aralkyl halides. However, extrapola tion of this reaction into aryl halides is not feasible C because the halogen atom attached to an aromatic nu I cleus is very difficult to remove therefrom. In copending Ser. No. 326,389, filed Nov. 27, 1963, there is disclosed C Xe c and claimed a method for the production of diaryl sul fides, dialkaryl sulfides and aryl alkaryl sulfides by re C C X x. X Ye acting at least one of an aryl halide and alkaryl halide with an alkali metal sulfide in a polar organic com . pound reaction medium. It has now been discovered 40 that an aromatic thiol can be produced when an excess N/ N/ l N/ of an alkali metal sulfide. (above equimolar) is added to IV a mono-halo-substituted aromatic compound in a polar wherein X is selected from the group consisting of chlo organic solvent. It has also been discovered that an aro rine, bronnine, fluorine and iodine, wherein R is selected matic sulfide is also produced. 45 from the group consisting of hydrogen and alkyl and It is an object of this invention to produce an aromatic cycloalkyl radicals containing from 1 to 6 carbon atoms, thiol. It is a further object of this invention to provide inclusive, wherein n, b, c and d are each whole integers a new and improved process for the production of aro selected from the group consisting of 0 and 1, wherein matic thiols and aromatic sulfides. It is a further object the sum b--c--d=1, and wherein not more than 4 sub of the invention to produce the aromatic thiols in a 50 Stituent groups other than hydrogen and halogen are substantial absence of water. present in the molecule. Other aspects, objects and the several advantages of Some examples of compounds having the above general the invention are apparent to one skilled in the art from formula are: Chlorobenzene a study of this disclosure and the appended claims. 55 4-chlorotoluene According to the invention, there is provided a process Bromobenzene for the production of aromatic thiols by the reaction of 1-chloro-3-ethylbenzene at least one nuclear monohalo-substituted aromatic com 1-fluoro-3-isopropylbenzene pound with an excess of an alkali metal sulfide, the re 1-iodo-2-methyl-4-ethylbenzene action being conducted in a polar organic solvent, at an 60 1-bromo-2,4-diethylbenzene elevated temperature and for a time sufficient to carry 1-chloro-3,4,5,6-tetramethylbenzene out the reaction. More specifically, the mol ratio of the 1-chloronaphthalene alkali metal sulfide to nuclear monohalo-substituted aro 4-chlorobiphenyl matic compounds should be at least 1.5, and preferably 2-bromobiphenyl above 2.0. 65 1-chloro-4-hexylbenzene 3,374,274 3. 4. 1-bromo-2,4,6-tri-n-butylbenzene covered that the percentage of aromatic thiols increases 4-bromo-p-terphenyl and the percentage of aromatic sulfides decreases with 6-cyclohexyl-1-chloronaphthalene increasing amounts of alkali metal sulfide. Thus, it can p-chlorobenzoic acid be seen that the amount of thiol or sulfide produced can 8-bromonaphthalene-carboxylic acid 5 be varied by simply varying the amount of alkali metal 4-trifluoromethylchlorobenzene sulfide added to the reactor. 4-methoxy-1-chloronaphthalene Typical aromatic thiols which can be prepared by this 4-n-hexoxy-1-fluorobenzene process include: 4-cyclopenEylthio-1-bromonaphthalene Benzenethiol (thiophenol) The alkali metal sulfides which can be employed in O 4-methylbenzenethiol the process of this invention are the monosulfides of so 4-carboxybenzenethiol dium, potassium, lithium, rubidium and cesium, includ 3-ethylbenzenethiol ing the anhydrous and hydrated forms of these sulfides. Naphthalenethiol The preferred sulfide is NaS and its hydrates. Biphenylthiol The polar organic solvent used in this invention is one 5 Terphenylthiol in which the halo-substituted aromatics and alkali metal 6-trifluoromethylnaphthalenethiol sulfides are at least partially soluble. A preferred class of solvents are amides. Specific examples of suitable Sol 2,3,4,5-tetramethylbenzenethiol vents include: N-methyl-2-pyrrollidone 20 Typical sulfides which can be prepared by this process Pyrrolidone include: Caprolactam Diphenyl sulfide N-ethylcaprolactam Di(4-methylphenyl) sulfide Dimethylacetamide 25 Di(3-ethylphenyl) sulfide Tetramethylurea Di (2-methyl-4-isopropylphenyl) sulfide Hexamethylphosphoramide Di(2,4-diethylphenyl) sulfide N,N'-ethylenedipyrrollidone Dinaphthyl sulfide Phenyl 4-methylphenyl sulfide The process of this invention is carried out by contact Di(2-ethyl-4-n-decylphenyl) sulfide ing the above-defined reactants in at least one polar sol 30 Phenyl naphthyl sulfide vent at a temperature of from about 125 C. to about Di(4-biphenylyl) sulfide 450° C., preferably from 175° C. to 350° C. The critical Di(4-p,p'-terphenylyl) sulfide feature is that an excess of alkali metal sulfide must be 4-biphenylyl phenyl sulfide used. Thus, the mol ratio of alkali metal sulfide to halo substituted aromatic compound should be at least 1.5, and preferably above 2.0. The pressure in the reaction Example Zone will generally be autogenous and this pressure can run as high as 1000 p.s. i. or greater, depending upon the A series of runs was carried out in which chloroben chosen reactants and polar solvent. Reaction times will zene was reacted with sodium sulfide to form thiophenol depend upon the chosen reaction temperature, with the 40 according to the process of this invention. longer reaction times being used at the lower temper In each of these runs, either 195 or 390 grams of Na2S atures and vice versa, Reaction times can vary from a containing 60 percent sulfide and 40 percent water was few minutes to several days. mixed with 1,300 ml. of N-methyl-2-pyrrollidone and 500 The amount of polar organic solvent in the reaction mi. of benzene and heated until essentially all of the Zone can vary over a wide range, but will generally range 65 water of hydration was removed. The benzene was also from about 100 to 2500 ml. of solvent per mol of alkali distilled off during this drying step. The resulting solu metal sulfide reactant, preferably about 250 ml. tion of alkali metal sulfide in N-methyl-2-pyrrollidone It is preferred to employ the substantially anhydrous (NMP) was then transferred to a reactor and an addi form of the alkali metal sulfides. The sulfides can be tional 200 ml. of NMP was used to rinse down the walls charged to the reaction zone in this form, or they can 50 of the reactor. 200 ml, of rinse was used in the first three be charged in a hydrated form, utilizing a drying pro runs and 600 ml. was used in the last run. The desired cedure to remove the water of hydration prior to charging amount of chlorobenzene was then added to the sulfide the halo-substituted aromatic compound. For example, a solvent solution after which the resulting mixture was hydrated form of the alkali metal sulfide can be mixed heated to 300° C. for 3 or 3.5 hours. At the end of this with the polar organic reaction solvent and heated to 55 time, the reaction mixture was cooled and worked up distill water off. This drying can be carried out by adding for recovery of thiophenol and attendant diphenyl sulfide an additional material such as benzene to the mixture by-product. prior to heating. Following the water removal, the result The reaction mixture was worked up by acidifying with ing solution of anhydrous sulfide in polar organic solvent 1:1 concentrated hydrochloric acid: water until acid to can be mixed with the desired halo-substituted aromatic 60 litmus, after which the acidified mixture was extracted compound.
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